WO2022138822A1 - 有機電界発光素子、有機ｅｌ表示装置、有機ｅｌ照明及び有機電界発光素子の製造方法 - Google Patents

有機電界発光素子、有機ｅｌ表示装置、有機ｅｌ照明及び有機電界発光素子の製造方法 Download PDF

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WO2022138822A1
WO2022138822A1 PCT/JP2021/047865 JP2021047865W WO2022138822A1 WO 2022138822 A1 WO2022138822 A1 WO 2022138822A1 JP 2021047865 W JP2021047865 W JP 2021047865W WO 2022138822 A1 WO2022138822 A1 WO 2022138822A1
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group
ring
substituent
formula
organic electroluminescent
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French (fr)
Japanese (ja)
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宏一朗 飯田
一毅 岡部
英貴 五郎丸
英司 小松
繁樹 服部
和弘 長山
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三菱ケミカル株式会社
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Priority to CN202180086334.3A priority Critical patent/CN116670145A/zh
Priority to JP2022571622A priority patent/JPWO2022138822A1/ja
Priority to KR1020237020236A priority patent/KR20230123948A/ko
Publication of WO2022138822A1 publication Critical patent/WO2022138822A1/ja

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/658—Organoboranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/115—Polyfluorene; Derivatives thereof

Definitions

  • the present invention relates to an organic electroluminescent device.
  • OLED organic electroluminescent device
  • An organic electroluminescent device usually has a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, etc. between an anode and a cathode, and materials suitable for each of these layers are being developed. Yes, the emission colors are red, green, and blue, and development is progressing for each.
  • examples of the method for forming the organic layer of the organic electroluminescent device include a vacuum vapor deposition method and a wet film formation method (coating method). Since the vacuum vapor deposition method is easy to stack, it has the advantages of improving charge injection from the anode and / or cathode and facilitating containment of excitons in the light emitting layer. On the other hand, the wet film forming method does not require a vacuum process, it is easy to increase the area, and by using a coating liquid in which a plurality of materials having various functions are mixed, a plurality of materials having various functions can be easily obtained. There are advantages such as being able to form a layer containing the above materials. Therefore, in recent years, research and development of an organic electroluminescent device by forming a film by a coating method has been energetically carried out.
  • Patent Documents 1 to 3 describe an organic electroluminescent element having a hole injection layer containing polystyrene sulfonic acid and a light emitting layer containing a light emitting material having a polycyclic heterocyclic compound skeleton containing boron and nitrogen. Have been described.
  • a polycyclic heterocyclic compound containing boron has an empty p-orbital on boron and easily reacts with various reactive groups. Therefore, the techniques disclosed in Patent Documents 1 to 3 are insufficient in reducing the drive voltage of the organic electroluminescent device, and the drive life cannot be improved. Since the holes disclosed in Patent Documents 1 to 3 use a hole injection layer containing a strongly acidic polystyrene sulfonic acid, many of the water and sulfonic acid groups taken in during the formation of the hole injection layer contain boron. It is considered that the cause is that it reacts with the ring heterocyclic compound while driving the element.
  • the present invention has been made in view of the above-mentioned conventional circumstances, and is an organic electroluminescent element having a light emitting layer containing a polycyclic heterocyclic compound containing boron, having a low driving voltage, and having a long driving life. Providing is an issue to be solved.
  • the present inventors contained a stable tetraarylborate ion satisfying the octet rule having no empty p orbital on boron, or a crosslinked product of an electron-accepting compound having a crosslinking group. It has been found that the above-mentioned problems can be solved by using the hole injection layer, and the present invention has been completed.
  • the gist of the present invention is as follows ⁇ 1> to ⁇ 28>.
  • An organic electroluminescent device having an anode, a cathode, a light emitting layer, and a hole injection layer.
  • the light emitting layer is provided between the anode and the cathode.
  • the hole injection layer is provided between the anode and the light emitting layer.
  • the light emitting layer contains a polycyclic heterocyclic compound represented by the following formula (1) and contains.
  • the hole injection layer is an organic electroluminescent device containing tetraarylborate ions.
  • Rings a, b, and c are independently aromatic hydrocarbon rings that may have substituents or aromatic heterocycles that may have substituents.
  • Y is O, NR or S
  • R is an aromatic hydrocarbon ring group which may have a substituent, an aromatic heterocyclic group or an alkyl group which may have a substituent.
  • the R is a carbon atom adjacent to an atom bonded to Y in at least one ring selected from the group consisting of the ring a, the ring b, and the ring c, and —O—, —S—, ⁇ . It may be bound by C (-R a ) 2- or a single bond.
  • Ra is a hydrogen atom or an alkyl group.
  • the adjacent carbon atom is not a carbon atom constituting the central fused bicyclic structure of the formula (1) containing B and Y.
  • At least one hydrogen atom in the polycyclic heterocyclic compound represented by the formula (1) may be substituted with a halogen atom or deuterium.
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently have an aromatic hydrocarbon ring group, a substituent and / or a cross-linking group which may have a substituent and / or a cross-linking group. May have an aromatic heterocyclic group, or an aromatic hydrocarbon ring group which may have a substituent and / or a bridging group, and an aromatic heterocyclic group which may have a substituent and / or a bridging group.
  • ⁇ 3> The organic electroluminescent device according to ⁇ 2>, wherein at least one of Ar 1 , Ar 2 , Ar 3 and Ar 4 in the formula (2) is a group represented by the following formula (3).
  • R 1 is an aromatic hydrocarbon ring group which may independently have a substituent and / or a cross-linking group, an aromatic heterocyclic group which may have a substituent and / or a cross-linking group, and a substituent.
  • Group, fluorine-substituted alkyl group, substituent or cross-linking group, F 4 indicates that four fluorine atoms are substituted.
  • F (5-m) indicates that each of them is independently substituted with 5m fluorine atoms.
  • the benzene ring and the naphthalene ring may have a substituent, and the substituents may be bonded to each other to form a ring.
  • R 110 in the formula (X4), the formula (X5), the formula (X6) and the formula (X10) each independently represents an alkyl group.
  • ⁇ 6> The organic electroluminescent device according to ⁇ 5>, wherein the cross-linking group is represented by any of the formulas (X1) to (X3).
  • ⁇ 7> The organic electroluminescent device according to any one of ⁇ 1> to ⁇ 6>, wherein the polycyclic heterocyclic compound represented by the above formula (1) is represented by the following formula (21).
  • Ring a, ring b and ring c are the same as those in the above formula (1).
  • Ring d and ring e have a structure in which two saturated hydrocarbon rings including B and two Y are condensed.
  • the ring f and the ring g are the same as the ring a, the ring b or the ring c, and each of them independently may have an aromatic hydrocarbon ring or a substituent which may have a substituent. It is a group heterocycle, Ring f is bonded to a carbon atom adjacent to an atom bonded to N in at least one ring of ring a and ring b by an —O—, —S—, —C (—R a ) 2- or single bond.
  • You may be Ring g is bonded to a carbon atom adjacent to an atom bonded to N in at least one ring of ring a and ring c by an —O—, —S—, —C (—R a ) 2- or single bond.
  • You may be Ra is a hydrogen atom or an alkyl group.
  • the adjacent carbon atoms are not the carbon atoms constituting the rings d and e including B and N, but At least one hydrogen atom in the polycyclic heterocyclic compound represented by the formula (21) may be substituted with a halogen atom or deuterium.
  • the organic electroluminescent device according to any one of ⁇ 1> to ⁇ 6>, wherein the polycyclic heterocyclic compound represented by the above formula (1) is represented by the following formula (71).
  • Each of A 1 to A 7 independently has a hydrogen atom, a fluorine atom, an alkyl group which may have a substituent, a heteroaryl group which is an electron-accepting substituent, a nitro group, a cyano group, or an electron.
  • Each of R 71 to R 78 may independently have a hydrogen atom, an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and a substituent.
  • An organic electroluminescent device having an anode, a cathode, a light emitting layer, and a hole injection layer.
  • the light emitting layer is provided between the anode and the cathode.
  • the hole injection layer is provided between the anode and the light emitting layer.
  • the light emitting layer contains a polycyclic heterocyclic compound represented by the following formula (1) and contains.
  • the hole injection layer is an organic electroluminescent device containing a crosslinked product of an electron-accepting compound having a crosslinking group.
  • Rings a, b, and c are independently aromatic hydrocarbon rings that may have substituents or aromatic heterocycles that may have substituents.
  • Y is O, NR or S
  • R is an aromatic hydrocarbon ring group which may have a substituent, an aromatic heterocyclic group or an alkyl group which may have a substituent.
  • the R is a carbon atom adjacent to an atom bonded to Y in at least one ring selected from the group consisting of the ring a, the ring b, and the ring c, and —O—, —S—, ⁇ . It may be bound by C (-R a ) 2- or a single bond.
  • Ra is a hydrogen atom or an alkyl group.
  • the adjacent carbon atom is not a carbon atom constituting the central fused bicyclic structure of the formula (1) containing B and Y. At least one hydrogen atom in the polycyclic heterocyclic compound represented by the formula (1) may be substituted with a halogen atom or deuterium. ) ⁇ 10>
  • the organic electroluminescent device according to ⁇ 9>, wherein the crosslinked group is represented by any of the following formulas (X1) to (X18).
  • the benzene ring and the naphthalene ring may have a substituent, and the substituents may be bonded to each other to form a ring.
  • R 110 in the formula (X4), the formula (X5), the formula (X6) and the formula (X10) each independently represents an alkyl group.
  • ⁇ 12> The organic electroluminescent device according to any one of ⁇ 9> to ⁇ 11>, wherein the polycyclic heterocyclic compound represented by the above formula (1) is represented by the following formula (21).
  • Ring a, ring b and ring c are the same as those in the above formula (1).
  • Ring d and ring e have a structure in which two saturated hydrocarbon rings including B and two Y are condensed.
  • the ring f and the ring g are the same as the ring a, the ring b or the ring c, and each of them independently may have an aromatic hydrocarbon ring or a substituent which may have a substituent. It is a group heterocycle, Ring f is bonded to a carbon atom adjacent to an atom bonded to N in at least one ring of ring a and ring b by an —O—, —S—, —C (—R a ) 2- or single bond.
  • You may be Ring g is bonded to a carbon atom adjacent to an atom bonded to N in at least one ring of ring a and ring c by an —O—, —S—, —C (—R a ) 2- or single bond.
  • You may be Ra is a hydrogen atom or an alkyl group.
  • the adjacent carbon atoms are not the carbon atoms constituting the rings d and e including B and N, but At least one hydrogen atom in the polycyclic heterocyclic compound represented by the formula (21) may be substituted with a halogen atom or deuterium.
  • the organic electroluminescent device according to any one of ⁇ 9> to ⁇ 11>, wherein the polycyclic heterocyclic compound represented by the above formula (1) is represented by the following formula (71).
  • Each of A 1 to A 7 independently has a hydrogen atom, a fluorine atom, an alkyl group which may have a substituent, a heteroaryl group which is an electron-accepting substituent, a nitro group, a cyano group, or an electron.
  • Each of R 71 to R 78 may independently have a hydrogen atom, an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and a substituent.
  • the dotted line means single bond or no bond.
  • An organic EL display device or an organic EL lighting comprising the organic electroluminescent element according to any one of ⁇ 1> to ⁇ 13>.
  • the method for manufacturing the organic electroluminescent device includes a step of forming the hole injection layer by a wet film formation method using a composition for forming a hole injection layer, and a wet film formation using the composition for forming a light emitting layer. It has a step of forming the light emitting layer by the method.
  • the composition for forming a hole injection layer contains tetraarylborate ion and an organic solvent.
  • the composition for forming a light emitting layer contains a polycyclic heterocyclic compound represented by the following formula (1) and an organic solvent.
  • Rings a, b, and c are independently aromatic hydrocarbon rings that may have substituents or aromatic heterocycles that may have substituents.
  • Y is O, NR or S
  • R is an aromatic hydrocarbon ring group which may have a substituent, an aromatic heterocyclic group or an alkyl group which may have a substituent.
  • the R is a carbon atom adjacent to an atom bonded to Y in at least one ring selected from the group consisting of the ring a, the ring b, and the ring c, and —O—, —S—, ⁇ . It may be bound by C (-R a ) 2- or a single bond.
  • Ra is a hydrogen atom or an alkyl group.
  • the adjacent carbon atom is not a carbon atom constituting the central fused bicyclic structure of the formula (1) containing B and Y. At least one hydrogen atom in the polycyclic heterocyclic compound represented by the formula (1) may be substituted with a halogen atom or deuterium.
  • the composition for forming a hole injection layer is a composition obtained through a step of dissolving or dispersing an electron-accepting ionic compound having a tetraarylborate ion structure and a hole transporting material in an organic solvent. , ⁇ 15>.
  • the method for manufacturing an organic electric field light emitting element ⁇ 17>
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently have an aromatic hydrocarbon ring group, a substituent and / or a cross-linking group which may have a substituent and / or a cross-linking group. May have an aromatic heterocyclic group, or an aromatic hydrocarbon ring group which may have a substituent and / or a bridging group, and an aromatic heterocyclic group which may have a substituent and / or a bridging group.
  • ⁇ 18> Manufacture of the organic electroluminescent device according to ⁇ 17>, wherein at least one of Ar 1 , Ar 2 , Ar 3 and Ar 4 in the above formula (2) is a group represented by the following formula (3).
  • R 1 is an aromatic hydrocarbon ring group which may independently have a substituent and / or a cross-linking group, an aromatic heterocyclic group which may have a substituent and / or a cross-linking group, and a substituent.
  • Group, fluorine-substituted alkyl group, substituent or cross-linking group, F 4 indicates that four fluorine atoms are substituted.
  • F (5-m) indicates that each of them is independently substituted with 5m fluorine atoms.
  • the benzene ring and the naphthalene ring may have a substituent, and the substituents may be bonded to each other to form a ring.
  • R 110 in the formula (X4), the formula (X5), the formula (X6) and the formula (X10) each independently represents an alkyl group.
  • ⁇ 21> The method for manufacturing an organic electroluminescent device according to ⁇ 20>, wherein the crosslinked group is represented by any of the formulas (X1) to (X3).
  • ⁇ 22> The production of the organic electroluminescent device according to any one of ⁇ 15> to ⁇ 21>, wherein the polycyclic heterocyclic compound represented by the above formula (1) is represented by the following formula (21). Method.
  • Ring a, ring b and ring c are the same as those in the above formula (1).
  • Ring d and ring e have a structure in which two saturated hydrocarbon rings including B and two Y are condensed.
  • the ring f and the ring g are the same as the ring a, the ring b or the ring c, and each of them independently may have an aromatic hydrocarbon ring or a substituent which may have a substituent. It is a group heterocycle, Ring f is bonded to a carbon atom adjacent to an atom bonded to N in at least one ring of ring a and ring b by an —O—, —S—, —C (—R a ) 2- or single bond.
  • You may be Ring g is bonded to a carbon atom adjacent to an atom bonded to N in at least one ring of ring a and ring c by an —O—, —S—, —C (—R a ) 2- or single bond.
  • You may be Ra is a hydrogen atom or an alkyl group.
  • the adjacent carbon atoms are not the carbon atoms constituting the rings d and e including B and N, but At least one hydrogen atom in the polycyclic heterocyclic compound represented by the formula (21) may be substituted with a halogen atom or deuterium.
  • ⁇ 23> The production of the organic electroluminescent device according to any one of ⁇ 15> to ⁇ 22>, wherein the polycyclic heterocyclic compound represented by the above formula (1) is represented by the following formula (71). Method.
  • Each of A 1 to A 7 independently has a hydrogen atom, a fluorine atom, an alkyl group which may have a substituent, a heteroaryl group which is an electron-accepting substituent, a nitro group, a cyano group, or an electron.
  • Each of R 71 to R 78 may independently have a hydrogen atom, an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and a substituent.
  • the dotted line means single bond or no bond.
  • a method for manufacturing an organic electroluminescent device having an anode, a hole injection layer, a light emitting layer, and a cathode in this order on a substrate includes a step of forming the hole injection layer by a wet film formation method using a composition for forming a hole injection layer, and a wet film formation using the composition for forming a light emitting layer. It has a step of forming the light emitting layer by the method.
  • the composition for forming a hole injection layer contains an electron-accepting compound having a cross-linking group and an organic solvent.
  • the composition for forming a light emitting layer contains a polycyclic heterocyclic compound represented by the following formula (1) and an organic solvent.
  • Rings a, b, and c are independently aromatic hydrocarbon rings that may have substituents or aromatic heterocycles that may have substituents.
  • Y is O, NR or S
  • R is an aromatic hydrocarbon ring group which may have a substituent, an aromatic heterocyclic group or an alkyl group which may have a substituent.
  • the R is a carbon atom adjacent to an atom bonded to Y in at least one ring selected from the group consisting of the ring a, the ring b, and the ring c, and —O—, —S—, ⁇ . It may be bound by C (-R a ) 2- or a single bond.
  • Ra is a hydrogen atom or an alkyl group.
  • the adjacent carbon atom is not a carbon atom constituting the central fused bicyclic structure of the formula (1) containing B and Y. At least one hydrogen atom in the polycyclic heterocyclic compound represented by the formula (1) may be substituted with a halogen atom or deuterium. ) ⁇ 25>
  • the benzene ring and the naphthalene ring may have a substituent, and the substituents may be bonded to each other to form a ring.
  • R 110 in the formula (X4), the formula (X5), the formula (X6) and the formula (X10) each independently represents an alkyl group.
  • ⁇ 26> The method for manufacturing an organic electroluminescent device according to ⁇ 25>, wherein the crosslinked group is represented by any of the formulas (X1) to (X3).
  • ⁇ 27> The production of the organic electroluminescent device according to any one of ⁇ 24> to ⁇ 26>, wherein the polycyclic heterocyclic compound represented by the above formula (1) is represented by the following formula (21). Method.
  • Ring a, ring b and ring c are the same as those in the above formula (1).
  • Ring d and ring e have a structure in which two saturated hydrocarbon rings including B and two Y are condensed.
  • the ring f and the ring g are the same as the ring a, the ring b or the ring c, and each of them independently may have an aromatic hydrocarbon ring or a substituent which may have a substituent. It is a group heterocycle, Ring f is bonded to a carbon atom adjacent to an atom bonded to N in at least one ring of ring a and ring b by an —O—, —S—, —C (—R a ) 2- or single bond.
  • You may be Ring g is bonded to a carbon atom adjacent to an atom bonded to N in at least one ring of ring a and ring c by an —O—, —S—, —C (—R a ) 2- or single bond.
  • You may be Ra is a hydrogen atom or an alkyl group.
  • the adjacent carbon atoms are not the carbon atoms constituting the rings d and e including B and N, but At least one hydrogen atom in the polycyclic heterocyclic compound represented by the formula (21) may be substituted with a halogen atom or deuterium.
  • ⁇ 28> The production of the organic electroluminescent device according to any one of ⁇ 24> to ⁇ 27>, wherein the polycyclic heterocyclic compound represented by the above formula (1) is represented by the following formula (71). Method.
  • Each of A 1 to A 7 independently has a hydrogen atom, a fluorine atom, an alkyl group which may have a substituent, a heteroaryl group which is an electron-accepting substituent, a nitro group, a cyano group, or an electron.
  • Each of R 71 to R 78 may independently have a hydrogen atom, an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and a substituent.
  • the dotted line means single bond or no bond.
  • the organic electroluminescent device of the present invention exhibits excellent device characteristics, particularly has a low drive voltage and a long drive life.
  • FIG. 1 is a schematic cross-sectional view showing a structural example of the organic electroluminescent device of the present invention.
  • an embodiment of an organic electroluminescent element, an organic EL display device including the organic electroluminescent element, and an organic EL lighting including the organic electroluminescent element, which is an embodiment of the present invention will be described in detail.
  • the following description is the first embodiment which is an example (representative example) of the embodiment of the present invention, but the present invention is not specified in these contents unless the gist thereof is exceeded.
  • the organic electroluminescent device according to the first embodiment of the present invention is an organic electroluminescent device having an anode, a cathode, a light emitting layer, and a hole injection layer.
  • the light emitting layer is provided between the anode and the cathode.
  • the hole injection layer is provided between the anode and the light emitting layer.
  • the light emitting layer contains a polycyclic heterocyclic compound represented by the following formula (1) and contains.
  • the hole injection layer contains tetraarylborate ions.
  • Rings a, b, and c are independently aromatic hydrocarbon rings that may have substituents or aromatic heterocycles that may have substituents.
  • Y is O, NR or S
  • R is an aromatic hydrocarbon ring group which may have a substituent, an aromatic heterocyclic group or an alkyl group which may have a substituent.
  • the R is a carbon atom adjacent to an atom bonded to Y in at least one ring selected from the group consisting of the ring a, the ring b, and the ring c, and —O—, —S—, ⁇ . It may be bound by C (-R a ) 2- or a single bond.
  • Ra is a hydrogen atom or an alkyl group.
  • the adjacent carbon atom is not a carbon atom constituting the central fused bicyclic structure of the formula (1) containing B and Y.
  • At least one hydrogen atom in the polycyclic heterocyclic compound represented by the formula (1) may be substituted with a halogen atom or deuterium.
  • Polycyclic heterocyclic compounds containing boron have an empty p-orbital on boron and are particularly susceptible to react with electron-donating substances. As a result of the reaction, an oxide of an electron-donating substance is generated, and this oxide may cause a further deterioration reaction during driving.
  • the tetraarylborate ion which has a stable structure satisfying the octet rule that does not have an empty p-orbital on boron, has the effect of stabilizing the cation in which the electron-donating substance is oxidized. Therefore, it is presumed that the deterioration reaction during driving can be suppressed by using tetraarylborate ion.
  • a polycyclic heterocyclic compound containing boron represented by the formula (1) is used for the light emitting layer, and a stable tetraarylborate ion satisfying the octet rule having no empty p-orbital on boron is used. It has been found that the above-mentioned problems can be solved by using the hole injection layer containing the above, and the first embodiment of the present invention has been completed.
  • the organic electroluminescent device according to the second embodiment of the present invention is an organic electroluminescent device having an anode, a cathode, a light emitting layer, and a hole injection layer.
  • the light emitting layer is provided between the anode and the cathode.
  • the hole injection layer is provided between the anode and the light emitting layer.
  • the light emitting layer contains a polycyclic heterocyclic compound represented by the following formula (1) and contains.
  • the hole injection layer contains a crosslinked product of an electron-accepting compound having a crosslinking group.
  • Rings a, b, and c are independently aromatic hydrocarbon rings that may have substituents or aromatic heterocycles that may have substituents.
  • Y is O, NR or S
  • R is an aromatic hydrocarbon ring group which may have a substituent, an aromatic heterocyclic group or an alkyl group which may have a substituent.
  • the R is a carbon atom adjacent to an atom bonded to Y in at least one ring selected from the group consisting of the ring a, the ring b, and the ring c, and —O—, —S—, ⁇ . It may be bound by C (-R a ) 2- or a single bond.
  • Ra is a hydrogen atom or an alkyl group.
  • the adjacent carbon atom is not a carbon atom constituting the central fused bicyclic structure of the formula (1) containing B and Y.
  • At least one hydrogen atom in the polycyclic heterocyclic compound represented by the formula (1) may be substituted with a halogen atom or deuterium.
  • Polycyclic heterocyclic compounds containing boron have an empty p-orbital on boron and are particularly susceptible to react with electron-donating substances.
  • a method of promoting hole injection from a metal anode and reducing a driving voltage by using an electron-accepting compound for the hole injection layer is used.
  • the electron-accepting compound of the hole-injecting layer diffuses and reaches the light emitting layer, and the electron-accepting compound. Is considered to have reacted with the polycyclic heterocyclic compound containing boron during device driving, leading to an increase in driving voltage and a reduction in driving life.
  • the electron-accepting compound contains a cross-linking group to promote the cross-linking reaction when the hole-injected layer is formed
  • the electron-accepting compound is fixed in the hole-injected layer. It is considered that the electron accepting compound does not diffuse when the layer above the hole injection layer is formed by the wet film forming method. Therefore, it is presumed that the deterioration reaction during driving can be suppressed by using an electron-accepting compound having a cross-linking group.
  • the boron-containing polycyclic heterocyclic compound represented by the formula (1) is used for the light emitting layer, and the hole injection layer is formed by using the electron-accepting compound having a cross-linking group, and has a cross-linking group. It has been found that the above-mentioned problems can be solved by using a hole injection layer containing a crosslinked product of an electron-accepting compound, and the second embodiment of the present invention has been completed.
  • the equation (1) in the organic electroluminescent device according to the first embodiment of the present invention and the equation (1) in the organic electroluminescent device according to the second embodiment of the present invention are the same and have a preferable range. The same is true for good substituents.
  • the light emitting layer contains a polycyclic heterocyclic compound represented by the above formula (1).
  • the polycyclic heterocyclic compound represented by the formula (1) is preferably a light emitting material.
  • the ring a, the ring b, and the ring c are each independently an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocycle which may have a substituent.
  • the substituent that the aromatic hydrocarbon ring or aromatic heterocycle may have is preferably a group selected from the following substituent group ⁇ .
  • the aromatic hydrocarbon ring or aromatic heterocycle has a central condensed bicyclic structure of formula (1) composed of B and Y (hereinafter, may be referred to as "central condensed bicyclic structure"). It is preferable to have a 5-membered ring or a 6-membered ring that shares a bond, and more preferably to have a 6-membered ring that shares a bond with the formula (1) central condensation bicyclic structure composed of B and Y.
  • the formula (1) central condensation bicyclic structure composed of B and Y means that the two saturated hydrocarbon rings composed of B and two Y shown in the center of the formula (1) are included. It is a condensed structure. Specifically, it is a structure in which the ring d and the ring e in the following formula (1') are condensed.
  • a 6-membered ring sharing a bond with the central condensed 2-ring structure means, for example, a case where the ring a is a benzene ring (6-membered ring).
  • the aromatic hydrocarbon ring or aromatic heterocycle (which is ring a) has this 6-membered ring” means that the ring a is formed only by the 6-membered ring or includes the 6-membered ring. As described above, it means that another ring or the like is condensed with this 6-membered ring to form the ring a.
  • ring b "ring c", and "5-membered ring”.
  • Examples of the aromatic hydrocarbon ring in the ring a, the ring b, and the ring c of the formula (1) include an aromatic hydrocarbon ring having 6 to 30 carbon atoms, and an aromatic hydrocarbon ring having 6 to 16 carbon atoms. Is preferable, an aromatic hydrocarbon ring having 6 to 12 carbon atoms is more preferable, and an aromatic hydrocarbon ring having 6 to 10 carbon atoms is particularly preferable.
  • aromatic hydrocarbon ring examples include a benzene ring which is a monocyclic system, a biphenyl ring which is a bicyclic system, a naphthalene ring which is a fused bicyclic system, and a terphenyl ring (m-terphenyl) which is a tricyclic system.
  • o-terphenyl, p-terphenyl fused tricyclics, ashenafutilene ring, fluorene ring, phenylene ring, phenanthrene ring, fused tetracyclic triphenylene ring, pyrene ring, naphthalene ring, fused pentacyclic system.
  • a certain pyrene ring or pentacene ring is preferable, a benzene ring, a biphenyl ring, a naphthalene ring, a terphenyl ring, or a fluorene ring is more preferable, and a benzene ring is most preferable.
  • Examples of the aromatic heterocycle in the ring a, the ring b and the ring c of the formula (1) include an aromatic heterocycle having 2 to 30 carbon atoms, and an aromatic heterocycle having 2 to 25 carbon atoms is preferable.
  • An aromatic heterocycle having 2 to 20 carbon atoms is more preferable, an aromatic heterocycle having 2 to 15 carbon atoms is further preferable, and an aromatic heterocycle having 2 to 10 carbon atoms is particularly preferable.
  • the "aromatic heterocycle” for example, a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms is preferable.
  • aromatic heterocycle examples include a pyrrole ring, an oxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, a thiathiazole ring, a triazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, and an indole ring.
  • Substituent group ⁇ is a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted diheteroarylamino group, a substituted or substituted group.
  • Unsubstituted aryl heteroarylamino group (amino group having aromatic hydrocarbon group and aromatic heterocyclic group), substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group , Or a halogen atom.
  • Substituents that may be possessed by a group selected from the substituent group ⁇ other than the halogen atom are selected from the following substituent group ⁇ .
  • Examples of the aromatic hydrocarbon group or aryl structure in the substituent group ⁇ include the group of the aromatic hydrocarbon ring in the ring a, the ring b and the ring c.
  • the specific structure and preferable structure of the aromatic hydrocarbon ring are the same as those of the aromatic hydrocarbon ring in the ring a, b and c of the formula (1).
  • the aromatic hydrocarbon group in the substituent group ⁇ is preferably a benzene ring.
  • Examples of the aromatic heterocyclic group or heteroaryl structure in the substituent group ⁇ include the group of the aromatic heterocycle in the rings a, b and c.
  • the specific structure of the aromatic heterocycle is the same as that of the aromatic heterocycle in the rings a, b and c of the formula (1).
  • the aromatic heterocyclic group in the substituent group ⁇ is preferably a triazine ring, a benzimidazole ring, a benzothiazole ring, a pyrimid [5,4-d] pyrimidine ring, or a benzo [1,2-d: 4,5-d]. ] It is a imidazole ring.
  • the alkyl group in the substituent group ⁇ may be either a straight chain or a branched chain, and examples thereof include a linear alkyl group having 1 to 24 carbon atoms and a branched chain alkyl group having 3 to 24 carbon atoms.
  • An alkyl group having 1 to 18 carbon atoms (branched chain alkyl group having 3 to 18 carbon atoms) is preferable, and an alkyl group having 1 to 12 carbon atoms (branched chain alkyl group having 3 to 12 carbon atoms) is more preferable.
  • alkyl group having 1 to 6 carbon atoms (branched alkyl group having 3 to 6 carbon atoms) is more preferable, and an alkyl group having 1 to 4 carbon atoms (branched chain alkyl group having 3 to 4 carbon atoms) is particularly preferable.
  • alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and an isopentyl group.
  • Examples include a group, an n-octyl group, a tert-octyl group and the like.
  • a part of the hydrogen atom of the alkyl group in the substituent group ⁇ may be replaced with a fluorine atom.
  • alkoxy group in the substituent group ⁇ examples include a straight chain having 1 to 24 carbon atoms or an alkoxy group having a branched chain having 3 to 24 carbon atoms.
  • Alkoxy groups having 1 to 18 carbon atoms are preferable, and alkoxy groups having 1 to 12 carbon atoms (alkoxy groups of branched chains having 3 to 12 carbon atoms) are more preferable.
  • Alkoxy groups having 1 to 6 carbon atoms are more preferable, and alkoxy groups having 1 to 4 carbon atoms (alkoxy groups of branched chains having 3 to 4 carbon atoms) are more preferable. Especially preferable.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group and a heptyloxy group. , Octyloxy group and the like.
  • halogen atom in the substituent group ⁇ examples include a fluorine atom, a chlorine atom, and a bromine atom. Fluorine atoms and chlorine atoms are preferable, and among them, fluorine atoms are more preferable.
  • the substituent group ⁇ is an aromatic hydrocarbon group optionally substituted with an aralkyl group, an aromatic heterocyclic group optionally substituted with an aralkyl group, an alkyl group or a halogen atom.
  • aromatic hydrocarbon group, aromatic heterocyclic group, alkyl group, aralkyl group, and halogen atom in the substituent group ⁇ include the same as those of the substituent group ⁇ , and the preferable structure is also the substituent group ⁇ . The same is true.
  • the substituent group ⁇ may be an aromatic hydrocarbon group optionally substituted with an aralkyl group, an aromatic heterocyclic group optionally substituted with an aralkyl group, an alkyl group, or an aralkyl group. Groups are preferred.
  • an aralkyl group which may be substituted with an aralkyl group, an aromatic hydrocarbon group or an aromatic heterocyclic group in the substituent group ⁇ , an aralkyl group having 7 to 30 carbon atoms is preferable.
  • a structure in which a benzene ring is bonded to an alkyl group is preferable.
  • (Y) Y in the formula (1) is O, NR or S.
  • (R) R is an aromatic hydrocarbon ring group which may have a substituent, an aromatic heterocyclic group or an alkyl group which may have a substituent.
  • the two Ys in the formula (1) may be the same or different from each other, but are preferably the same.
  • the two Ys are preferably NR.
  • R of the formula (1) is an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent
  • the rings a, b and c of the formula (1) It is a group similar to an aromatic hydrocarbon ring group which may have a substituent in the above or an aromatic heterocyclic group which may have a substituent.
  • Specific structures and preferred structures also include aromatic hydrocarbon ring groups which may have substituents on rings a, b and c of formula (1) or aromatic heterocyclic groups which may have substituents. The same is true.
  • R in the formula (1) is an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent
  • the formula (1) is represented by the following formula (21). Will be done.
  • the formula (1) preferably has a structure represented by the following formula (21).
  • Examples of the alkyl group in R of the formula (1) include an alkyl group in the substituent group ⁇ .
  • an alkyl group having 1 to 4 carbon atoms for example, a methyl group, an ethyl group, etc. is particularly preferable.
  • R is a carbon atom adjacent to an atom bonded to Y in at least one ring selected from the group consisting of the ring a, the ring b, and the ring c, and —O—, —S—, —C. (-R a ) 2 -or may be bonded by a single bond.
  • Ra is a hydrogen atom or an alkyl group.
  • the alkyl group in Ra include an alkyl group in the substituent group ⁇ .
  • an alkyl group having 1 to 4 carbon atoms is particularly preferable, and for example, a methyl group, an ethyl group and the like.
  • the adjacent carbon atoms are not carbon atoms constituting the central condensed bicyclic structure of the formula (1) containing B and Y.
  • at least one hydrogen atom in the polycyclic heterocyclic compound represented by the formula (1) may be substituted with a halogen atom or deuterium.
  • Ring a, ring b and ring c are the same as those in the above formula (1).
  • Ring d and ring e have a structure in which two saturated hydrocarbon rings including B and two Y are condensed.
  • the ring f and the ring g are the same as the ring a, the ring b or the ring c, and each of them independently may have an aromatic hydrocarbon ring or a substituent which may have a substituent. It is a group heterocycle, Ring f is bonded to a carbon atom adjacent to an atom bonded to N in at least one ring of ring a and ring b by an —O—, —S—, —C (—R a ) 2- or single bond.
  • You may be Ring g is bonded to a carbon atom adjacent to an atom bonded to N in at least one ring of ring a and ring c by an —O—, —S—, —C (—R a ) 2- or single bond.
  • You may be Ra is a hydrogen atom or an alkyl group.
  • the adjacent carbon atoms are not the carbon atoms constituting the rings d and e including B and N, but At least one hydrogen atom in the polycyclic heterocyclic compound represented by the formula (21) may be substituted with a halogen atom or deuterium.
  • the aromatic hydrocarbon ring group and the aromatic heterocyclic group in the ring f and the ring g include an aromatic hydrocarbon ring group having 6 to 10 carbon atoms (for example, a phenyl group, a naphthyl group, etc.) and a carbon number of 2 to 15 carbon atoms.
  • Aromatic heterocyclic groups eg, carbazolyl groups, etc. are preferred.
  • rings f and g which are aromatic hydrocarbon rings or aromatic heterocycles, may have are the same as those of rings a, b and c, and are preferably from the substituent group ⁇ . It is the group to be selected.
  • Equation (22) The formula (21) preferably has a structure represented by the following formula (22).
  • Ring a, ring b, ring c, ring d and ring e in the above formula (21) all have a benzene ring structure.
  • Ring a, ring b, ring c, ring d and ring e may have a substituent.
  • Ring f is bonded to a carbon atom adjacent to an atom bonded to N in at least one ring of ring a and ring b by an —O—, —S—, —C (—R a ) 2- or single bond.
  • You may be Ring g is bonded to a carbon atom adjacent to an atom bonded to N in at least one ring of ring a and ring c by an —O—, —S—, —C (—R a ) 2- or single bond.
  • You may be Ra is a hydrogen atom or an alkyl group.
  • At least one hydrogen atom in the polycyclic heterocyclic compound represented by the formula (22) may be substituted with a halogen atom or deuterium.
  • the aromatic compound represented by the formula (22) is a polycyclic heterocyclic compound represented by the formula (71) described later or a polycyclic heterocyclic compound represented by the formula (81) described later. Is also preferable.
  • the aromatic compound represented by the formula (1) is a polycyclic heterocyclic compound represented by the formula (71) described later or a polycyclic heterocyclic compound represented by the formula (81) described later. It is also preferable to have.
  • the polycyclic heterocyclic compound represented by the formula (71) described later provides a green to red light emitting material having a long light emitting wavelength capable of expanding the color reproduction range. It is preferable because it can be done.
  • the polycyclic heterocyclic compound represented by the formula (81) described later can provide a blue light emitting material having a short emission wavelength capable of expanding the color reproduction range. preferable.
  • the structure of the polycyclic heterocyclic compound represented by the formula (1) is not particularly limited, and examples thereof include the following structures.
  • the polycyclic heterocyclic compound represented by the formula (1) is also preferably a polycyclic heterocyclic compound represented by the following formula (71).
  • the polycyclic heterocyclic compound represented by the following formula (71) may be referred to as a polycyclic heterocyclic compound TD1.
  • Each of A 1 to A 7 independently has a hydrogen atom, a fluorine atom, an alkyl group which may have a substituent, a heteroaryl group which is an electron-accepting substituent, a nitro group, a cyano group, or an electron.
  • Each of R 71 to R 78 may independently have a hydrogen atom, an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and a substituent.
  • the dotted line means single bond or no bond.
  • the electron cloud of LUMO is localized and gathered at the position where A 1 to A 7 are bonded to the phenyl group. Therefore, by using at least one selected from A 1 to A 7 as an electron acceptor-type substituent, the electron cloud spreads, the energy level of LUMO is stabilized, and the energy difference between HOMO and LUMO becomes small. .. As a result, by using the polycyclic heterocyclic compound represented by the formula (71), it is possible to obtain an emission spectrum having a longer wavelength.
  • Each of A 1 to A 7 independently has a hydrogen atom, a fluorine atom, an alkyl group which may have a substituent, a heteroaryl group which is an electron-accepting substituent, a nitro group, a cyano group, or an electron. It is an aromatic hydrocarbon group or an aromatic heterocyclic group having a heteroaryl group, a nitro group or a cyano group as substituents having an accepting property.
  • At least one selected from A 1 to A 7 is an electron-accepting substituent, and A 1 to A 7 other than the electron-accepting substituent are independently hydrogen atoms and fluorine, respectively. It is an atom or an alkyl group which may have a substituent.
  • the emission wavelength can be adjusted depending on the number and type of A 1 to A 7 , which is preferable.
  • An electron-accepting substituent is a substituent having a chemical structure that tends to have an excess of electrons by extracting electrons from adjacent chemical structures by chemically bonding.
  • the electron-accepting substituent examples include a substituent such as a heteroaryl group, a nitro group and a cyano group, an aromatic hydrocarbon group having the above substituent, an aromatic heterocyclic group and the like. Of these, a heteroaryl group is preferable from the viewpoint of lengthening the wavelength.
  • a heteroaryl group is an aryl group having at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom.
  • Examples of the heteroaryl group include groups having 1 to 4 rings of polycyclic aromatic heteroaryls containing a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and the like.
  • the electron acceptor substituent has an absolute value of the value obtained by adding the energy level of HOMO and the energy level of LUMO and dividing by 2 (hereinafter, may be referred to as "absolute value ⁇ ") of 3 eV or more. It is preferably a group that is. When the absolute value ⁇ is 3 eV or more, the electron acceptor property of the substituent is empirically improved.
  • the absolute value ⁇ of the electron acceptor substituent is preferably 3.1 eV or more, more preferably 3.5 eV or more, and even more preferably 4.0 eV or more. Further, although the upper limit of the absolute value ⁇ in the electron acceptor substituent is not particularly set, it is generally 7.0 eV or less.
  • the energy level of HOMO and the energy level of LUMO in the electron accepting substituent are the energy level of the molecular orbital of HOMO and the energy level of the molecular orbital of LUMO obtained as follows. That is, the single bond between the electron-accepting substituent in the formula (1) and the adjacent phenyl group is deleted, and a hydrogen atom is added. Then, if the molecular structure of the obtained electron-accepting substituent is calculated by the molecular orbital calculation software Gaussian16 using the general function: B3LYP and the basic function: 6-31G (d), the structure is optimized by the density general function. good.
  • the electron acceptor substituent is a group represented by the following formula (5), a group represented by the following formula (6), a group represented by the following formula (7), or a group represented by the following formula (8). It is preferably the group represented.
  • R 732 to R 745 are each independently a hydrogen atom, an alkyl group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-hexyl group and n-.
  • alkyl group examples include linear, branched, or cyclic alkyl groups having 1 or more and 24 or less carbon atoms, such as an octyl group, a cyclohexyl group, and a dodecyl group.
  • the aromatic hydrocarbon group examples include an aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, and the like.
  • examples thereof include a monovalent group of a 6-membered monocyclic ring or a 2 to 5 fused ring such as a pyrene ring, a benzpyrene ring, a chrysen ring, a triphenylene ring, an acenaften ring, a fluorantene ring, and a fluorene ring.
  • R 732 to R 745 may have can be selected from the substituent group Z2 described later.
  • the electron acceptor substituent is preferably the group represented by the above formula (5) from the viewpoint of lengthening the wavelength and easiness of production by organic synthesis.
  • the group represented by the above formula (5) has a relatively large absolute value ⁇ and has less steric hindrance with the adjacent phenyl group in the above formula (71), so that the adjacent phenyl group and the above formula (5) are used.
  • the twist of the ⁇ plane of the represented group is small, and the effect of lengthening the large emission wavelength can be obtained.
  • the group represented by the above formula (5) can be produced relatively easily in organic synthesis, and even when it is desired to improve the solubility in a solvent, it has a long chain (for example, 4 carbon atoms) in R 732 and R 733 .
  • the above) alkyl group can be introduced relatively easily.
  • an alkyl group which may have a substituent is preferable from the viewpoint of increasing the absolute value ⁇ to facilitate the acquisition of a long wavelength emission wavelength and also from the viewpoint of solubility in a solvent. Further, it is more preferable that at least one selected from R 732 and R 733 is a phenyl group having a tert-butyl group.
  • one selected from R 732 and R 733 is an alkyl group which may have a substituent, and the other is an alkyl group.
  • Aromatic hydrocarbon groups that may have substituents are preferred.
  • the substituent that the aromatic hydrocarbon group may have can be selected from the substituent group Z2.
  • a 1 to A 7 other than the electron-accepting substituent are alkyl groups which may independently have a hydrogen atom, a fluorine atom, or a substituent.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-hexyl group and n-.
  • alkyl group examples include linear, branched, or cyclic alkyl groups having 1 or more and 24 or less carbon atoms, such as an octyl group, a cyclohexyl group, and a dodecyl group.
  • the substituents that A 1 to A 7 may have can be selected from the substituent group Z2 described later.
  • a 1 to A 7 are each independently a fluorine atom or an alkyl group which may have a substituent
  • a 1 to A 7 are hydrogen atoms due to their electron acceptability. Since the emission wavelength is slightly shorter or longer than in the case, it is preferable to select a substituent according to the target wavelength.
  • a 1 to A 7 are each independently long-chain alkyl groups for the purpose of improving the solubility in a solvent.
  • At least one selected from A 1 , A 4 , and A 7 is preferably an electron acceptor-type substituent, and more preferably a group represented by the formula (5).
  • both A 1 and A 7 are electron acceptor substituents, almost the same wavelength lengthening effect can be obtained as compared with the case where only A 4 is the same electron acceptor substituent. Further, it is preferable that two or more selected from A 1 to A 7 are electron acceptor substituents because the wavelength becomes longer, and two or more selected from A 1 to A 7 are electron acceptor property. It is preferable that the substituent is a substituent and at least one of them is an electron acceptor - type substituent because the wavelength is further extended.
  • the single bond connecting the adjacent phenyl groups A 1 to A 7 is twisted, and the ⁇ plane of the adjacent phenyl group and the main aromatic hydrocarbon group of the electron acceptor-type substituent is formed. It is preferable not to twist it. This twist makes it difficult for the charges of the adjacent phenyl group and the electron acceptor-type substituent to be exchanged smoothly, and it becomes difficult for the emission wavelength of the above formula (71) to be lengthened.
  • R 71 to R 78 may independently have a hydrogen atom, an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and a substituent.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-hexyl group and n-.
  • alkyl group examples include linear, branched, or cyclic alkyl groups having 1 or more and 24 or less carbon atoms, such as an octyl group, a cyclohexyl group, and a dodecyl group.
  • the aromatic hydrocarbon group examples include an aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, and the like.
  • examples thereof include a monovalent group of a 6-membered monocyclic ring or a 2 to 5 fused ring such as a pyrene ring, a benzpyrene ring, a chrysen ring, a triphenylene ring, an acenaften ring, a fluorantene ring, and a fluorene ring.
  • the aromatic heterocyclic group preferably has an aromatic heterocyclic group having 3 or more and 60 or less carbon atoms, and specifically, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, or an imidazole ring.
  • Oxadiazole ring indole ring, carbazole ring, pyrrolobymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, flopyrol ring, furan ring, thienoflan ring, benzoisoxazole ring, benzoisothiazole ring, Benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxalin ring, phenanthridine ring, benzoimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene.
  • Examples thereof include monovalent groups of 5- or 6-membered monocyclic rings or 2-
  • R 71 to R 78 may have can be selected from the substituent group Z2 described later.
  • At least one selected from R 71 to R 78 is an electron donor substituent from the viewpoint of lengthening the wavelength.
  • An electron donor substituent is a substituent having a chemical structure that is liable to become electron deficient by donating electrons from adjacent chemical structures by chemically bonding.
  • the electron cloud of HOMO is localized and gathered at R 71 to R 78 . Therefore, by using at least one selected from R 71 to R 78 as an electron donor substituent, the electron cloud of HOMO is likely to spread outward, the energy level of HOMO is destabilized, and HOMO is formed. The energy difference of LUMO becomes small. As a result, the polycyclic heterocyclic compound represented by the formula (71) can obtain an emission spectrum having a long wavelength.
  • the electron donor substituent is preferably a group having an absolute value ⁇ of less than 3 eV.
  • the absolute value ⁇ is less than 3 eV, the electron donor property of the substituent is empirically improved.
  • the absolute value ⁇ of the electron donor substituent is more preferably less than 2.97 eV, further preferably less than 2.8 eV, and particularly preferably less than 2.6 eV from the viewpoint of lengthening the wavelength. Further, although the lower limit of the absolute value ⁇ in the electron donor substituent is not particularly set, it is generally 1 eV or more.
  • the HOMO energy level and the LUMO energy level in the electron donor substituent are the HOMO molecular orbital energy level and the LUMO molecular orbital energy level obtained as follows. That is, the single bond between the electron donor substituent in the formula (1) and the adjacent phenyl group is deleted, and a hydrogen atom is added. Then, if the molecular structure of the obtained electron donor substituent is calculated by the density general function using the molecular orbital calculation software Gaussian16 using the general function: B3LYP and the basic function: 6-31G (d). good.
  • the electron donor substituent is preferably a group represented by the following formula (2), a group represented by the following formula (3), or a group represented by the following formula (4).
  • Each of R 709 to R 731 is an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or a hydrogen atom, respectively.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-hexyl group and n-.
  • alkyl group examples include linear, branched, or cyclic alkyl groups having 1 or more and 24 or less carbon atoms, such as an octyl group, a cyclohexyl group, and a dodecyl group.
  • the aromatic hydrocarbon group examples include an aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, and the like.
  • examples thereof include a monovalent group of a 6-membered monocyclic ring or a 2 to 5 fused ring such as a pyrene ring, a benzpyrene ring, a chrysen ring, a triphenylene ring, an acenaften ring, a fluorantene ring, and a fluorene ring.
  • R 709 to R 731 may have can be selected from the substituent group Z2 described later.
  • the electron donor substituent is preferably the group represented by the above formula (2) from the viewpoint of lengthening the wavelength, ease of production by organic synthesis, and balance of structural stability.
  • the group represented by the above formula (2) has a relatively small absolute value ⁇ , and the effect of lengthening the emission wavelength can be obtained. Further, the group represented by the above formula (2) can be produced relatively easily in organic synthesis, and even when it is desired to improve the solubility in a solvent, a long-chain alkyl group is compared with R 709 to R 716 . It can be easily introduced.
  • At least one selected from R 709 to R 716 is preferably a tert-butyl group from the viewpoint of solubility in a solvent and ease of synthesis.
  • each of R 71 to R 78 independently has an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and an aromatic which may have a substituent.
  • the emission wavelength is slightly shorter or longer than that in the case where R 71 to R 78 are hydrogen atoms due to their electrophilicity. It is preferable to select the substituent according to the wavelength of.
  • R 71 to R 78 are each independently long-chain alkyl groups for the purpose of improving the solubility in a solvent.
  • the dotted line may be a single bond or no bond.
  • the dotted line is preferably a single bond.
  • the electron cloud spreads and the emission wavelength becomes slightly longer.
  • the dotted line is a single bond, it becomes easy to introduce an electron acceptor substituent in A 1 to A 7 and an electron donor substituent in R 71 to R 78 .
  • the polycyclic heterocyclic compound of the above formula (71) is an asymmetric type because it has an effect of narrowing the half width of the emission wavelength. It is considered that the half-value width of the emission spectrum is narrowed because the polycyclic heterocyclic compounds are less likely to associate with each other due to the asymmetric type and the symmetry is lowered, and the interaction between the polycyclic heterocyclic compounds is lowered.
  • the polycyclic heterocyclic compound is an asymmetric type when it is rotated by 180 ° with respect to the axis of rotation when the line connecting the bond axis of B and A4 is used as the axis of rotation in the above equation (71). It does not have the same structure, or it is not mirror-symmetric with respect to a plane perpendicular to the plane formed by the polycyclic heterocycle of the compound of the above formula (71) including the axis of rotation.
  • a 1 and A 7 are different, A 2 and A 6 are different, A 3 and A 5 are different, R 71 and R 78 are different, R 72 and R 77 are different, R 73 .
  • R 76 are different, or R 74 and R 75 are different, the structure.
  • substituent group Z2 examples include the following structures.
  • a linear, branched, or cyclic alkyl group usually having 1 or more carbon atoms, preferably 4 or more carbon atoms, usually 24 or less, preferably 12 or less carbon atoms; for example, a methyl group, an ethyl group, or n-.
  • the number of carbon atoms is usually 2 or more, and usually 24.
  • An alkenyl group which is less than or equal to, preferably 12 or less; for example, a vinyl group or the like.
  • Aalkoxy group for example, a methoxy group, an ethoxy group, etc.
  • the above is usually 24 or less, preferably 12 or less dialkylamino groups; for example, dimethylamino group, diethylamino group, etc., which usually have 10 or more carbon atoms, preferably 12 or more, and usually 36 or less.
  • diarylamino group for example, a diphenylamino group, a ditrilamino group, an N-carbazolyl group, etc., an arylalkylamino group having a carbon number of usually 7 or more, usually 36 or less, preferably 24 or less;
  • an acyl group such as a phenylmethylamino group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less; for example, a halogen atom such as an acetyl group or a benzoyl group; for example, a fluorine atom or a chlorine atom.
  • a syroxy group preferably 3 or more, usually 36 or less, preferably 24 or less; for example, a trimethylsiloxy group, a triphenylsiloxy group, etc., which has 6 or more carbon atoms, usually 36 or less, and preferably 36 or less.
  • Is 24 or less aromatic hydrocarbon groups for example, phenyl groups
  • Aromatic heterocyclic groups having a carbon number of usually 3 or more, preferably 4 or more, usually 36 or less, preferably 24 or less; for example, a thienyl group, a pyridyl group, etc. having 7 or more carbon atoms.
  • -1-phenylmethyl group 1,1-di (n-hexyl) -1-phenylmethyl group, 1,1-di (n-octyl) -1-phenylmethyl group, phenylmethyl group, phenylethyl group, 3 -Phenyl-1-propyl group, 4-phenyl-1-n-butyl group, 1-methyl-1-phenylethyl group, 5-phenyl-1-n-propyl group, 6-phenyl-1-n-hexyl group , 6-naphthyl-1-n-hexyl group, 7-phenyl-1-n-heptyl group, 8-phenyl-1-n-octyl group, 4-phenylcyclohexyl group, etc.
  • polycyclic heterocyclic compound TD1 ⁇ Specific example of polycyclic heterocyclic compound TD1>
  • the structure of the polycyclic heterocyclic compound TD1 represented by the formula (71) is not particularly limited, and examples thereof include the following structures.
  • the polycyclic heterocyclic compound represented by the formula (1) is also preferably a polycyclic heterocyclic compound represented by the following formula (81).
  • the polycyclic heterocyclic compound represented by the following formula (81) may be referred to as a polycyclic heterocyclic compound TD2.
  • R 81 and four R 82 each independently have a hydrogen atom, an alkyl group having 10 or less carbon atoms which may have a substituent, and a carbon number which may have a substituent. It represents an aromatic heterocyclic group having 3 or more and 20 or less carbon atoms which may have an aromatic hydrocarbon group of 6 or more and 20 or less or a substituent.
  • a 81 represents a structure represented by the following formula (82). a80, b80, c80, and d80 each independently represent an integer of 0 to 2, and at least one of a80 to d80 is an integer of 1 or more. When there are a plurality of A 81s in the formula (81), the plurality of A 81s may be the same or different.
  • the asterics (*) represent the joint and represent the joint.
  • RF represents a fluoroalkyl group having 5 or less carbon atoms.
  • R 83 may have an alkyl group having 10 or less carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 or more carbon atoms and 20 or less carbon atoms which may have a substituent, or a carbon which may have a substituent.
  • e80 represents an integer from 0 to 5.
  • the two RFs in equation (82) may be the same or different.
  • the plurality of R 83s may be the same or different.
  • the polycyclic heterocyclic compound represented by the above formula (81) has a condensed heterocyclic skeleton containing a boron atom and a nitrogen atom as a basic skeleton, and the two fluoros represented by the above formula (82) are added to this basic skeleton. It is characterized in that at least one quaternary carbon atom substituted with an alkyl group and a benzene ring is connected.
  • the fluorine atom which is a strong electron-withdrawing group
  • the basic skeleton so that ionization has a great influence on the element characteristics of the organic electric field light emitting element. It is possible to shorten the emission wavelength without significantly changing the potential and electron affinity.
  • the polycyclic heterocyclic compound of the present invention has a structure. Excellent solubility in organic solvents. Therefore, the film produced by the wet film forming method has high uniformity and is suitable as a light emitting material for an organic electroluminescent element.
  • R 81 and R 82 Each of the R 81 and the four R 82s in the formula (81) independently has a hydrogen atom, an alkyl group having 10 or less carbon atoms which may have a substituent, and 6 carbon atoms which may have a substituent. It represents an aromatic heterocyclic group having 3 or more and 20 or less carbon atoms which may have an aromatic hydrocarbon group or a substituent having 20 or less.
  • alkyl groups having 10 or less carbon atoms examples include methyl group, ethyl group, branched, linear or cyclic propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group and adamantyl group. Can be mentioned.
  • R 1 is an alkyl group having 10 or less carbon atoms, a methyl group, a branched, linear or cyclic propyl group or a butyl group is preferable, and a branched butyl group is particularly preferable, from the viewpoint of the stability of the compound. ..
  • aromatic hydrocarbon groups having 6 or more and 20 or less carbon atoms include monovalent groups such as a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a chrysen ring, a pyrene ring, a benzoanthracene ring, and a perylene ring. From the viewpoint of solubility of the compound, a phenyl group, which is a monovalent group of the benzene ring, is preferable.
  • aromatic heterocyclic groups having 3 or more and 20 or less carbon atoms include monovalent groups such as a pyridine ring, a quinoline ring, a benzofuran ring, and a carbazole ring.
  • R 81 a hydrogen atom and an alkyl group having 1 to 4 carbon atoms are preferable, and a hydrogen atom or a t-butyl group is more preferable.
  • a hydrogen atom is preferable as R 82 .
  • a80, b80, c80, and d80 each independently represent an integer of 0 to 2, and at least one of a80 to d80 is an integer of 1 or more. From the viewpoint of the short emission wavelength of the compound, a80 + b80 + c80 + d80 is preferably 2 or more, and a80 + b80 + c80 + d80 is particularly preferably 4 or more.
  • RF represents a fluoroalkyl group having 5 or less carbon atoms.
  • fluoroalkyl groups having 5 or less carbon atoms include perfluoroalkyl groups such as trifluoromethyl group, pentafluoroethyl group, branched, linear or cyclic perfluoropropyl group, perfluorobutyl group and perfluoropentane group. From the viewpoint of the film-forming property of the compound, a trifluoromethyl group and a pentafluoroethyl group are preferable, and a trifluoromethyl group is particularly preferable.
  • R 83 contains an alkyl group having 10 or less carbon atoms which may have a substituent, and an aromatic hydrocarbon group or a substituent having 6 or more and 20 or less carbon atoms which may have a substituent. It represents an aromatic heterocyclic group having 3 or more and 20 or less carbon atoms which may be possessed.
  • the alkyl group having 10 or less carbon atoms include a methyl group, an ethyl group, a branched, linear or cyclic propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, and a decyl group.
  • a branched or linear propyl group, butyl group, pentyl group or hexyl group is preferable, and a branched or linear butyl group, branched, linear or cyclic hexyl group is particularly preferable. ..
  • aromatic hydrocarbon groups having 6 or more and 20 or less carbon atoms include monovalent groups such as a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a chrysen ring, a pyrene ring, a benzoanthracene ring, and a perylene ring. From the viewpoint of solubility of the compound, a phenyl group, which is a monovalent group of the benzene ring, is preferable.
  • aromatic heterocyclic groups having 3 or more and 20 or less carbon atoms include monovalents such as a pyridine ring, a quinoline ring, a benzofuran ring, and a carbazole ring.
  • R 81 to R 83 may have> R 81 , R 82 , and R 83 have an alkyl group having 10 or less carbon atoms which may have a substituent, and an aromatic hydrocarbon group or a substituent having 6 or more and 20 or less carbon atoms which may have a substituent.
  • an aromatic heterocyclic group having 3 or more and 20 or less carbon atoms which may be possessed examples of the substituent which the alkyl group, the aromatic hydrocarbon group and the aromatic heterocyclic group may have are described later. It can be selected from the substituent group W1.
  • an alkyl group having 10 or less carbon atoms, an aromatic hydrocarbon group or an aromatic heterocyclic group having 20 or less carbon atoms, and an aralkyl group having 30 or less carbon atoms are preferable, and an alkyl group having 10 or less carbon atoms is more preferable.
  • An aromatic hydrocarbon group having 20 or less carbon atoms, and an aralkyl group having 30 or less carbon atoms are preferable, and an alkyl group having 10 or less carbon atoms is more preferable.
  • Examples of an alkyl group having 10 or less carbon atoms as a substituent include a methyl group and an ethyl group, as well as a branched, linear and cyclic propyl group, a butyl group, a pentyl group, a pentyl group, a hexyl group, an octyl group and a nonyl group. , A decyl group. From the viewpoint of the stability of the compound, a methyl group, an ethyl group, a branched group, a linear group, a cyclic propyl group and a butyl group are preferable, and a branched propyl group is particularly preferable.
  • aromatic hydrocarbon groups having 6 or more and 20 or less carbon atoms as substituents include monovalent rings such as benzene ring, naphthalene ring, phenanthren ring, anthracene ring, chrysen ring, pyrene ring, benzoanthracene ring and perylene ring.
  • a group is mentioned, and from the viewpoint of solubility of the compound, a phenyl group which is a monovalent group of a benzene ring is preferable.
  • Examples of the aromatic heterocyclic group having 3 or more carbon atoms and 20 or less carbon atoms as a substituent include a monovalent group such as a pyridine ring, a quinoline ring, a benzofuran ring, and a carbazole ring.
  • Examples of an aralkyl group having 30 or less carbon atoms as a substituent include a benzyl group, a 2-phenylethyl group, a 2-phenylpropyl-2-yl group, a 2-phenylbutyl-2-yl group, and a 3-phenylpentyl-. 3-yl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group, 7-phenyl-1-heptyl group, Examples thereof include a 8-phenyl-1-octyl group.
  • substituent group W1 examples include the following structures. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, dodecyl group and the like.
  • a linear, branched, or cyclic alkyl group usually having 1 or more carbon atoms, preferably 4 or more, usually 24 or less, preferably 12 or less;
  • Aralkill group For example, an alkoxy group such as a methoxy group or an ethoxy group having a carbon number of usually 1 or more, usually 24 or less, preferably 12 or less;
  • an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group, which usually has 2 or more carbon atoms and usually has 24 or less, preferably 12 or less carbon atoms;
  • the alkyl group, the aromatic hydrocarbon group or the aromatic heterocyclic group is preferable, and the alkyl group and the aromatic hydrocarbon group are more preferable. From the viewpoint of charge transportability, it is more preferable to have no substituent.
  • each substituent of the above-mentioned substituent group W1 may further have a substituent.
  • substituents the same ones as those of the above-mentioned substituents (substituent group W1) can be used.
  • the polycyclic complex compound TD2 represented by the above formula (81) preferably has a structure represented by the following formula (83).
  • R 81 , R 82 , and A 81 are synonymous with R 81 , R 82 , and A 81 in equation (81).
  • a83, b83, c83 and d83 are independently 0 or 1, and at least one is 1.
  • the light emitting layer further preferably contains a host material.
  • the host material is preferably a charge-transporting host material, and materials conventionally used as materials for an organic electroluminescent device can be used. For example, pyridine, carbazole, naphthalene, perylene, pyrene, anthracene, chrysene, naphthalene, phenanthrene, coronen, fluoranthene, benzophenanthrene, fluorene, acetonaftofluoranthene, coumarin, p-bis (2-phenylethenyl) benzene and theirs.
  • One of these may be used alone, or two or more of them may be used in any combination and ratio.
  • naphthalene, perylene, pyrene, anthracene, chrysene, naphthacene, phenanthrene, coronene, fluoranthene, benzophenanthrene, fluorene, acetonaftofluoranthene and derivatives thereof are preferable, and anthracene derivatives are more preferable. ..
  • anthracene derivative As the anthracene derivative, a compound represented by the following formula (30) is preferable.
  • Ar 241 and Ar 242 have structures independently represented by the following formula (31), Ar 243 represents a substituent, and Ar 243 is different even if they are the same when there are a plurality of them. It may be, and n 43 is an integer of 0 to 8.
  • Ar 244 and Ar 245 each independently represent an aromatic hydrocarbon structure which may have a substituent or a heteroaromatic ring structure which may have a substituent.
  • n 44 is an integer of 1 to 5
  • n 45 is an integer of 0 to 5.
  • Ar 244 is preferably an aromatic hydrocarbon structure which is a monocyclic or fused ring having 6 to 30 carbon atoms, which may have a substituent, and more preferably may have a substituent.
  • An aromatic hydrocarbon structure which is a monocyclic or fused ring having 6 to 12 carbon atoms.
  • the aromatic hydrocarbon structure is more preferably a benzene ring structure, a naphthalene structure, an anthracene structure, or a phenanthrene structure, and further preferably a benzene ring structure.
  • Ar 245 preferably has an aromatic hydrocarbon structure which is a monocyclic or fused ring having 6 to 30 carbon atoms, which may have a substituent, or may have a substituent, which may have 6 carbon atoms. It is an aromatic heterocyclic structure which is a fused ring of to 30 and more preferably an aromatic hydrocarbon structure which is a monocycle or a fused ring having 6 to 12 carbon atoms which may have a substituent, or It is an aromatic heterocyclic structure which is a fused ring having 12 carbon atoms which may have a substituent.
  • aromatic hydrocarbon structure a benzene ring structure, a naphthalene structure, an anthracene structure, a phenanthrene structure, and as an aromatic heterocyclic structure, a dibenzofuran structure, a dibenzothiophene structure, and a phenanthroline structure are more preferable, and an aromatic hydrocarbon structure is preferable.
  • aromatic hydrocarbon structure a benzene ring structure, naphthalene structure, phenanthrene structure, and aromatic heterocyclic structure, a dibenzofuran structure and a phenanthrene structure are more preferable.
  • n 44 is preferably an integer of 1 to 3, more preferably 1 or 2, and n 45 is preferably 0 to 3, more preferably 0 to 2.
  • the substituents Ar 243 and Ar 244 and Ar 245 may have are preferably a group selected from the following substituent group Z, and more preferably an alkyl group or aroma contained in the substituent group Z. It is a group hydrocarbon group, more preferably an aromatic hydrocarbon group contained in the substituent group Z.
  • the substituent group Z includes an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkoxycarbonyl group, a dialkylamino group, a diallylamino group, an arylalkylamino group, an acyl group and a halogen atom. It is a group consisting of a haloalkyl group, an alkylthio group, an arylthio group, a silyl group, a siloxy group, a cyano group, an aromatic hydrocarbon group, and an aromatic heterocyclic group. These substituents may contain any of linear, branched and cyclic structures.
  • the substituent group Z has the following structure.
  • a cyclic alkyl group For example, a linear, branched, or cyclic alkenyl group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less, such as a vinyl group;
  • an alkoxy group such as a methoxy group or an ethoxy group having a carbon number of usually 1 or more, usually 24 or less, and preferably 12 or less;
  • an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group, which usually has 2 or more carbon atoms, usually 24 or less, and preferably 12 or less carbon atoms
  • an acyl group such as an acetyl group or a benzoyl group having a carbon number of usually
  • an alkyl group, an alkoxy group, a diarylamino group, an aromatic hydrocarbon group, or an aromatic heterocyclic group is preferable.
  • an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable, and it is more preferable that the aromatic hydrocarbon group does not have a substituent.
  • an alkyl group or an alkoxy group is preferable.
  • each substituent of the above-mentioned substituent group Z may further have a substituent.
  • substituents include the same substituents as the above-mentioned substituents (substituent group Z).
  • Each substituent that the substituent group Z may have is preferably an alkyl group having 8 or less carbon atoms, an alkoxy group having 8 or less carbon atoms, or a phenyl group, and more preferably an alkyl group having 6 or less carbon atoms. It is an alkoxy group or a phenyl group having 6 or less carbon atoms, and it is more preferable that each of the substituents of the substituent group Z does not have a further substituent from the viewpoint of charge transportability.
  • the compound represented by the formula (30) is a low molecular weight material, and the molecular weight is preferably 3,000 or less, more preferably 2,500 or less, particularly preferably 2,000 or less, and most preferably 1. , 500 or less, usually 300 or more, preferably 350 or more, and more preferably 400 or more.
  • the structure of the anthracene derivative represented by the formula (30) is not particularly limited, but for example, the following structure is preferable.
  • the light emitting layer may be formed by either a vacuum vapor deposition method or a wet film forming method, but a wet film forming method is preferable.
  • the light emitting layer is formed by applying a light emitting layer forming composition containing an organic solvent and drying it.
  • the composition for forming a light emitting layer contains a polycyclic heterocyclic compound represented by the above formula (1) and an organic solvent.
  • the composition for forming a light emitting layer preferably further contains a host material.
  • Organic solvent contained in the composition for forming a light emitting layer is a volatile liquid component used for forming a layer containing a polycyclic heterocyclic compound by wet film formation.
  • the organic solvent is not particularly limited as long as it is an organic solvent in which the polycyclic heterocyclic compound and the charge transporting compound which are solutes are well dissolved.
  • Preferred organic solvents include, for example, alkanes such as n-decane, cyclohexane, ethylcyclohexane, decalin, bicyclohexane; aromatic hydrocarbons such as toluene, xylene, mesitylene, phenylcyclohexane, tetraline, methylnaphthalene; chlorobenzene, di.
  • alkanes such as n-decane, cyclohexane, ethylcyclohexane, decalin, bicyclohexane
  • aromatic hydrocarbons such as toluene, xylene, mesitylene, phenylcyclohexane, tetraline, methylnaphthalene
  • chlorobenzene di.
  • Halogenized aromatic hydrocarbons such as chlorobenzene and trichlorobenzene; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetol, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3 -Aromatic ethers such as dimethylanisole, 2,4-dimethylanisole and diphenyl ether; aromatic esters such as phenylacetate, phenylpropionate, methyl benzoate, ethyl benzoate, propyl benzoate and n-butyl benzoate; Aromatic ketones such as cyclohexanone, cyclooctanone, fencon; alicyclic alcohols such as cyclohexanol and cyclooctanol; aliphatic ketones such as methylethylketone and dibutylketone; aliphatic alcohols such
  • alkanes, aromatic hydrocarbons and aromatic esters are preferable, and aromatic hydrocarbons and aromatic esters are particularly preferable.
  • One type of these organic solvents may be used alone, or two or more types may be used in any combination and ratio.
  • the boiling point of the organic solvent used is usually 80 ° C. or higher, preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and usually 350 ° C. or lower, preferably 330 ° C. or lower, more preferably 300 ° C. or lower. If the boiling point of the organic solvent is lower than this range, the film formation stability may decrease due to solvent evaporation from the light emitting layer forming composition during wet film formation. If the boiling point of the organic solvent exceeds this range, the film formation stability may decrease due to the solvent remaining after the film formation during the wet film formation.
  • organic solvents it is considered preferable to combine two or more organic solvents having a boiling point of 150 ° C. or higher because it is easy to form a more uniform coating film.
  • the content of the polycyclic heterocyclic compound represented by the formula (1) in the composition for forming a light emitting layer is usually 0.001% by mass or more, preferably 0.01% by mass or more, and usually 30.0% by mass or less. It is preferably 20.0% by mass or less.
  • the content of the compound represented by the formula (30) in the composition for forming a light emitting layer is usually 0.01% by mass or more, preferably 0.1% by mass or more, usually 30.0% by mass or less, preferably 20. It is 0% by mass or less.
  • the content of the host material contained in the light emitting layer forming composition is usually 0.01% by mass or more, preferably 0.1% by mass or more, usually 30.0% by mass or less, preferably 20.0% by mass or less. be.
  • the content of the host material contained in the composition for forming a light emitting layer is usually 1000 parts by mass or less, preferably 100 parts by mass or less, more preferably 100 parts by mass or less, relative to 1 part by mass of the polycyclic heterocyclic compound represented by the formula (1). It is preferably 50 parts by mass or less, usually 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and more preferably 1 part by mass or more.
  • the content of the organic solvent contained in the composition for forming a light emitting layer is usually 10% by mass or more, preferably 50% by mass or more, particularly preferably 80% by mass or more, and usually 99.95% by mass or less, preferably 99. It is 9% by mass or less, particularly preferably 99.8% by mass or less.
  • the content of the organic solvent is at least the above lower limit, the viscosity is appropriate and the coatability is improved, and when it is at least the above upper limit, a uniform film can be easily obtained and the film forming property is good.
  • the composition for forming a light emitting layer may contain other compounds in addition to the above compounds.
  • Preferred examples of the other compound include phenols such as dibutylhydroxytoluene and dibutylphenol, which are known as antioxidants.
  • the method for forming the light emitting layer is preferably a wet film forming method.
  • the wet film forming method is a method in which a composition is applied to form a liquid film, and the film is dried to remove an organic solvent to form a film of a light emitting layer.
  • the coating method include spin coating method, dip coating method, die coating method, bar coating method, blade coating method, roll coating method, spray coating method, capillary coating method, inkjet method, nozzle printing method, screen printing method, and gravure.
  • a wet film forming method such as a printing method or a flexographic printing method is adopted, and the coating film is dried to form a film.
  • a spin coating method, a spray coating method, an inkjet method, a nozzle printing method and the like are preferable.
  • an inkjet method or a nozzle printing method is preferable, and an inkjet method is particularly preferable.
  • the drying method is not particularly limited, but natural drying, vacuum drying, heat drying, or vacuum drying while heating can be appropriately used.
  • the heat drying may be carried out after natural drying or vacuum drying to further remove the residual organic solvent.
  • the pressure it is preferable to reduce the pressure to a value equal to or lower than the vapor pressure of the organic solvent contained in the composition for forming a light emitting layer.
  • the heating method is not particularly limited, but heating with a hot plate, heating in an oven, infrared heating, etc. can be used.
  • the heating time is usually 80 ° C. or higher, preferably 100 ° C. or higher, more preferably 110 ° C. or higher, further preferably 200 ° C. or lower, still more preferably 150 ° C. or lower.
  • the heating time is usually preferably 1 minute or more, 2 minutes or more, usually 60 minutes or less, 30 minutes or less, and even more preferably 20 minutes or less.
  • the hole injection layer Since the hole injection layer needs to have a function of transporting holes, it contains a hole transporting material.
  • the hole transport material contained in the hole injection layer should contain a cationic radical site. Is preferable.
  • An electron-accepting compound is used to form the hole-injected layer in order to cation radicalize the hole-transporting material.
  • an ionic compound composed of tetraarylborate ion which is an anion having an ionic value of 1 and a counter cation, which will be described later, is preferable because it has high stability.
  • Cation radicalization of hole transport material is performed as follows.
  • a compound having a triarylamine structure for example, when tetraarylborate having diaryliodonium as a counter cation is used as an electron-accepting compound, the following formula is used when forming the hole injection layer.
  • the counter cation can change from diaryliodonium to triarylaminium.
  • Ar and Ar 1 to Ar 4 each independently have an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent. It is a monovalent group in which a plurality of structures selected from an aromatic hydrocarbon ring group which may be present and an aromatic heterocyclic group which may have a substituent are linked.
  • the tetraarylborate having triarylaminium as a counter cation is an electron-accepting compound. ..
  • a compound composed of a cation and an anion of the hole transporting material, tetraarylborate ion is referred to as a charge transporting ion compound. Details will be described later.
  • Electrode-accepting compound with cross-linking group examples include those having an ionic compound composed of tetraarylborate ion and a counter cation as a mother skeleton as described above.
  • the cross-linking group of the electron-accepting compound which forms a cross-linked product of the electron-accepting compound having a cross-linking group contained in the hole injection layer of the organic electric field light emitting element according to the second embodiment of the present invention is heat and / or A group that reacts with another group located in the vicinity of the crosslinked group to form a new chemical bond by irradiation with an active energy ray.
  • the reacting group may be the same group as the cross-linking group or a different group.
  • cross-linking group a cross-linking group represented by any of the following formulas (X1) to (X18) is preferable.
  • the benzene ring and the naphthalene ring may have a substituent. Further, the substituents may be bonded to each other to form a ring.
  • R 110 in the formula (X4), the formula (X5), the formula (X6) and the formula (X10) represents an alkyl group which may independently have a substituent.
  • the alkyl group represented by R 110 has a linear, branched or cyclic structure, and has 1 or more carbon atoms, preferably 24 or less, more preferably 12 or less, still more preferably 8 or less.
  • the benzene ring and naphthalene ring of the formulas (X1) to (X4), the alkyl group and the aromatic hydrocarbon are preferable as the substituents that the R 110 of the formulas (X4) to (X6) and (X10) may have. It is a group, an alkyloxy group, and an aromatic group.
  • the alkyl group as a substituent has a linear, branched or cyclic structure, and has a carbon number of preferably 24 or less, more preferably 12 or less, still more preferably 8 or less, and preferably 1 or more.
  • the carbon number of the aromatic hydrocarbon group as a substituent is preferably 24 or less, more preferably 18 or less, still more preferably 12 or less, and preferably 6 or more.
  • the aromatic hydrocarbon group may further have the alkyl group as a substituent.
  • the number of carbon atoms of the alkyloxy group as a substituent is preferably 24 or less, more preferably 12 or less, still more preferably 8 or less, and preferably 1 or more.
  • the carbon number of the aralkyl group as a substituent is preferably 30 or less, more preferably 24 or less, still more preferably 14 or less, and preferably 7 or more.
  • the alkylene group contained in the aralkyl group preferably has a linear or branched structure.
  • the aryl group contained in the aralkyl group may further have the alkyl group as a substituent.
  • the cross-linking group represented by any of the formulas (X1) to (X3) is preferable because the cross-linking reaction proceeds only by heat, the polarity is small, and the influence on charge transport is small.
  • the cyclobutene ring is opened by heat as shown in the following formula, and the opened groups are bonded to each other to form a crosslinked structure.
  • the cyclobutene ring is opened by heat as shown in the following formula, and the opened groups are bonded to each other to form a crosslinked structure.
  • the cyclobutene ring is opened by heat as shown in the following formula, and the opened groups are bonded to each other to form a crosslinked structure.
  • the crosslinked group represented by any of the formulas (X1) to (X3) has a cyclobutene ring opened by heat, and the opened group reacts with a double bond when a double bond is present in the vicinity.
  • the following shows an example in which the crosslinked group represented by the formula (X1) forms a crosslinked structure with the group having an open ring and the crosslinked group represented by the formula (X4) having a double bond site. (However, R 110 of the formula (X4) is not shown.)
  • Examples of the group containing a double bond capable of reacting with the cross-linking group represented by any of the formulas (X1) to (X3) include the cross-linking group represented by the formula (X4) and the formula (X5). Examples thereof include a cross-linking group represented by any one of (X6), (X12), (X15), (X16), (X17) and (X18).
  • any of the formulas (X1) to (X3) may be added to other components forming the hole injection layer such as a hole transporting compound. It is preferable to contain a cross-linking group represented by (1) because the possibility of forming a cross-linking structure increases.
  • the cross-linking group represented by any of the radically polymerizable formulas (X4), (X5) and (X6) is preferable because it has a small polarity and does not easily interfere with charge transport.
  • the cross-linking group represented by the formula (X7) is preferable in that it enhances electron acceptability.
  • the cross-linking group represented by the formula (X7) is used, the following cross-linking reaction proceeds.
  • crosslinking group represented by any of the formulas (X8) and (X9) is preferable because of its high reactivity.
  • the cross-linking group represented by the formula (X8) and the cross-linking group represented by the formula (X9) are used, the following cross-linking reaction proceeds.
  • cross-linking group a cross-linking group represented by any of the cationically polymerizable formulas (X10), (X11) and (X12) is preferable because of its high reactivity.
  • the hole injection layer of the organic electric field light emitting element of the present invention is preferably obtained by wet-forming a composition for forming a hole injection layer, and the composition for forming a hole injection layer will be described later. It is preferable that the composition is obtained through a step of dissolving or dispersing a first ionic compound having a tetraarylborate ion structure and a hole transporting material described later in an organic solvent.
  • the hole transport layer of the organic electric field light emitting element of the present invention contains a charge transporting ionic compound having the tetraarylborate ion structure of the present invention as an anion and the cation of the hole transport material as a counter cation, which will be described later. Is preferable.
  • the electron-accepting compound in the electron-accepting compound having a cross-linking group an electron-accepting compound which is an ionic compound is preferable, and the ionic compound as an electron-accepting compound is an ionic compound having a tetraarylborate ion structure as an anion. Is preferable.
  • the electron-accepting compound is an ionic compound having a tetraarylborate ion structure as an anion, it is preferable that the tetraarylborate ion has a cross-linking group. The tetraarylborate ion structure will be described later.
  • the cross-linked product of the electron-accepting compound having a cross-linking group includes the case of the following cross-linked product.
  • -A compound in which tetraarylborate ions in the present invention are crosslinked.
  • -A compound in which the tetraarylborate ion and the hole transport material in the present invention are crosslinked.
  • the "tetraarylborate ion in the present invention” is a case where it exists as an electron-accepting compound which is an ionic compound composed of a tetraarylborate ion and a counter cation described later, and a tetraarylborate ion described later. This includes the case where it exists as a charge-transporting ionic compound composed of a cation of a hole-transporting material.
  • the two cross-linking groups that undergo a cross-linking reaction may be the same cross-linking group or different cross-linking groups as long as the cross-linking reaction is possible.
  • the tetraarylborate ion may have four substituents and / or an aromatic hydrocarbon ring or a substituent and / or an aromatic group on the boron atom. It is an anion having an ionic value of 1 substituted with a heterocycle.
  • the tetraarylborate ion contained in the organic electric field light emitting device of the present invention has a fluorine atom or a fluorine-substituted alkyl group as a substituent of the aryl group from the viewpoint of further improving the stability. That is, it is preferably expressed by the following formula (2).
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently have an aromatic hydrocarbon ring group, a substituent and / or a cross-linking group which may have a substituent and / or a cross-linking group. May have an aromatic heterocyclic group, or an aromatic hydrocarbon ring group which may have a substituent and / or a bridging group, and an aromatic heterocyclic group which may have a substituent and / or a bridging group.
  • At least one of Ar 1 , Ar 2 , Ar 3 and Ar 4 preferably has a cross-linking group.
  • aromatic hydrocarbon ring group used for Ar 1 , Ar 2 , Ar 3 and Ar 4 a single ring or a 2 to 6 fused ring is preferable.
  • a single ring and 2 to 6 fused rings are preferable.
  • a monovalent group or a biphenyl group derived from a benzene ring, a naphthalene ring, a fluorene ring, a pyridine ring or a carbazole ring is more preferable because of its excellent stability and heat resistance.
  • it is a monovalent group derived from a benzene ring, that is, a phenyl group or a biphenyl group.
  • a plurality of structures selected from an aromatic hydrocarbon ring group which may have a substituent and / or a cross-linking group and an aromatic heterocyclic group which may have a substituent and / or a cross-linking group are linked 1.
  • the total number of monocyclic or 2 to 6 fused ring aromatic hydrocarbon ring groups and monocyclic or 2 to 6 fused ring aromatic heterocyclic groups contained in the valence group is 2 or more and 8 or less. Is preferable, 4 or less is more preferable, and 3 or less is more preferable.
  • Examples of the substituents that Ar 1 , Ar 2 , Ar 3 and Ar 4 may have include the groups described in the substituent group W described later.
  • a fluorine atom or a fluorine-substituted alkyl group is preferable from the viewpoint of increasing the stability of the anion and improving the effect of stabilizing the cation.
  • the fluorine atom or the fluorine-substituted alkyl group is preferably substituted with two or more of Ar 1 , Ar 2 , Ar 3 and Ar 4 , and more preferably with three or more. It is preferable to replace it with four, and it is most preferable to replace it with four.
  • a linear or branched alkyl group having 1 to 12 carbon atoms and having a fluorine atom substituted is used.
  • a perfluoroalkyl group is more preferred, a linear or branched perfluoroalkyl group having 1 to 5 carbon atoms is even more preferred, and a linear or branched perfluoroalkyl group having 1 to 3 carbon atoms is particularly preferred.
  • Methyl groups are most preferred. The reason for this is that the hole injection layer containing the crosslinked product of the tetraarylborate ion or the electron-accepting compound having a cross-linking group and the coating film laminated on the hole-injected layer become stable.
  • cross-linking groups that Ar 1 , Ar 2 , Ar 3 and Ar 4 may have are the same as the cross-linking groups.
  • the tetraarylborate ion contained in the organic electric field light emitting device of the present invention further increases the stability of the anion and further enhances the effect of stabilizing the cation.
  • at least one of Ar 3 and Ar 4 is a group represented by the formula (3), and at least two of Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently represented by the formula (3). It is more preferable that the group is a group, and it is further preferable that at least three of Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently represented by the formula (3), and Ar 1 , Ar 2 , Ar 3 are more preferable. It is most preferable that all of Ar 4 and Ar 4 are independently represented by the formula (3).
  • R 1 is an aromatic hydrocarbon ring group which may independently have a substituent and / or a cross-linking group, an aromatic heterocyclic group which may have a substituent and / or a cross-linking group, and a substituent.
  • Group, fluorine-substituted alkyl group, substituent or cross-linking group, F 4 indicates that four fluorine atoms are substituted.
  • F (5-m) indicates that each of them is independently substituted with 5m fluorine atoms.
  • k represents an integer of 0 to 5 independently of each other.
  • m represents an integer of 0 to 5 independently of each other.
  • K is preferably 1 or more, and more preferably 2 or more, in that the stability of the anion is further improved. 0 or 1 is preferable, and 0 is preferable because k is easy to disperse without bias.
  • m is preferably 0 in that it is more excellent in durability, preferably 1 or more in that various functions can be introduced into tetraarylborate ions, and further preferably 1 or 2 in terms of compatibility with durability. It is preferable that k + m ⁇ 1 in that the stability of the anion is improved and the durability is also excellent.
  • the preferable structure and the substituent which may be possessed are the structures of Ar 1 , Ar 2 , Ar 3 and Ar 4 and may have. Similar to the substituent.
  • Examples of the substituent of R 1 and the substituent when R 1 is a substituent include the groups described in the substituent group W described later.
  • At least one R 1 is preferably a fluorine-substituted alkyl group, preferably a perfluoroalkyl group, in that the stability of the anion is further increased and the effect of stabilizing the cation is further improved. It is preferably present, and more preferably a trifluoromethyl group.
  • the cross-linking group of R 1 and the cross-linking group when R 1 is a cross-linking group are as described above.
  • At least one R 1 contains the cross-linking group from the viewpoint of achieving both cross-linking property and electron accepting property.
  • the cross-linking group is the cross-linking group, or one or more of the cross-linking groups are bonded to an aromatic hydrocarbon group.
  • R 1 is a group represented by the following formula (4) or a group containing a group represented by the following formula (5).
  • the group represented by the formula (4) and the group represented by the formula (5) may have a substituent, and as an example of the substituent, the group represented by R 1 may have a substituent. Is the same as.
  • the R1 is a group represented by the formula (4) or a group represented by the formula (5), or a group represented by the formula (4) or a group represented by the formula (5).
  • a structure in which one or more are bonded to an aromatic hydrocarbon group is preferable.
  • R 1 has a structure in which one or more of the cross-linking groups are bonded to an aromatic hydrocarbon group
  • the aromatic hydrocarbon group is selected from a benzene ring, a naphthalene ring, or a benzene ring and a naphthalene ring. It is preferable that the structure is such that two or more of them are concatenated, and the number of concatenations is preferably 4 or less.
  • R 1 is more preferably a structure in which the cross-linking group is bonded to a benzene ring monocycle or a naphthalene ring monocycle, and further preferably a structure in which the cross-linking group is bonded to the benzene ring. It is particularly preferable that the cross-linking group has one or two bonds.
  • R 1 is a group represented by the formula (4) or a group containing a group represented by the following formula (5)
  • a more preferable R 1 is a benzene ring monocycle or a naphthalene ring monocycle of the formula (4).
  • the group represented by the formula (5) is bonded to the benzene ring, and the group represented by the formula (4) or the group represented by the formula (5) is bonded to the benzene ring.
  • the structure has one or two bonds, and the group represented by the formula (4) or the group represented by the formula (5) is particularly preferably bonded.
  • the group represented by the formula (4) and the group represented by the formula (5) have crosslinkability, and it is considered that the tetraarylborate ion and the counter cation do not diffuse into other layers, which is preferable.
  • the substituent group W includes a hydrogen atom, a halogen atom, a cyano group, an aromatic hydrocarbon ring group consisting of 1 to 5 aromatic hydrocarbon rings, an aliphatic hydrocarbon ring group, an alkyl group, an alkenyl group, and an alkynyl group. It is an aralkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylketone group or an arylketone group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and the fluorine atom is preferable from the viewpoint of the stability of the compound. From the viewpoint of compound stability, it is particularly preferable that four or more fluorine atoms are substituted.
  • Examples of the aromatic ring hydrocarbon group consisting of 1 to 5 aromatic hydrocarbon rings include a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a naphthyl group, a phenanthrenyl group, a triphenylene group, and a naphthylphenyl group.
  • a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group or a quaterphenyl group is preferable because of the stability of the compound.
  • Examples of the aliphatic hydrocarbon ring group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
  • the alkyl group usually has 1 or more carbon atoms, preferably 4 or more, usually 24 or less, preferably 12 or less, still more preferably 8 or less, and more preferably 6 or less.
  • a group, a 2-ethylhexyl group, a dodecyl group and the like can be mentioned.
  • the alkenyl group usually has 2 or more carbon atoms, usually 24 or less, and preferably 12 or less. Specific examples thereof include a vinyl group, a propenyl group, a butenyl group and the like.
  • the alkynyl group usually has 2 or more carbon atoms, usually 24 or less, preferably 12 or less, and specific examples thereof include an acetyl group, a propynyl group, and a butynyl group.
  • aralkyl group examples include a benzyl group, a phenylethyl group, a phenylhexyl group and the like.
  • the alkoxy group usually has 1 or more carbon atoms, usually 24 or less, preferably 12 or less, more preferably 6 or less, and specific examples thereof include a methoxy group, an ethoxy group, a butyloxy group, and a hexyloxy group. Groups, octyloxy groups and the like can be mentioned.
  • the aryloxy group usually has 4 or more carbon atoms, preferably 5 or more, more preferably 6 or more, usually 36 or less, preferably 24 or less, still more preferably 12 or less. Specific examples thereof include a phenoxy group and a naphthyloxy group.
  • the alkylthio group usually has 1 or more carbon atoms, usually 24 or less, preferably 12 or less, and specific examples thereof include a methylthio group, an ethylthio group, a butylthio group, and a hexylthio group.
  • the arylthio group usually has 4 or more carbon atoms, preferably 5 or more, usually 36 or less, preferably 24 or less, and specific examples thereof include a phenylthio group and a naphthylthio group.
  • the alkyl ketone group usually has 1 or more carbon atoms, usually 24 or less, preferably 12 or less, more preferably 6 or less, and specific examples thereof include an acetyl group, an ethylcarbonyl group, and a butylcarbonyl group. , Octylcarbonyl group and the like.
  • the aryl ketone group usually has 5 or more carbon atoms, preferably 7 or more, usually 25 or less, preferably 13 or less, and specific examples thereof include a benzoyl group and a naphthylcarbonyl group. ..
  • adjacent substituents may be bonded to each other to form a ring.
  • ring formation examples include a cyclobutene ring, a cyclopentene ring and the like.
  • substituents may be further substituted with a substituent, and examples of the substituent include a halogen atom, an alkyl group, an aryl group or the above-mentioned cross-linking group.
  • a halogen atom or an aryl group is preferable in terms of compound stability.
  • the halogen atom is most preferable, and the fluorine atom is preferable among the halogen atoms.
  • the compounds of (A-1) and (A-2) are preferable in terms of electron acceptability, heat resistance, and solubility. Further, since it is highly stable as a composition for a charge transport film, (A-18), (A-19), (A-20), (A-21), (A-25), (A-26). ), (A-28) are more preferable, and (A-19), (A-21), (A-25), (A-26), and (A-28) are particularly preferable because of the stability of the organic electroluminescent device. preferable.
  • the tetraarylborate ion is also preferably used as an electron-accepting ion compound containing a tetraarylborate ion.
  • An electron-accepting ionic compound containing a tetraarylborate ion is referred to as a first ionic compound.
  • the first ionic compound consists of the tetraarylborate ion, which is an anion, and a counter cation.
  • the first ionic compound is used as an electron accepting compound.
  • an iodonium cation, a sulfonium cation, a carbo cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptylrienyl cation or a ferrosenium cation having a transition metal is preferable, and an iodonium cation, a sulfonium cation, a carbo cation, Ammonium cations are more preferred, and iodonium cations are particularly preferred.
  • the iodonium cation is preferably a structure represented by the general formula (6) described later, and a more preferable structure is also the same.
  • the iodonium cations include diphenyliodonium cation, bis (4-tert-butylphenyl) iodonium cation, 4-tert-butoxyphenylphenyliodonium cation, 4-methoxyphenylphenyliodonium cation, and 4-isopropylphenyl-4-methyl. Phenyliodonium cations and the like are preferred.
  • sulfonium cation triphenylsulfonium cation, 4-hydroxyphenyldiphenylsulfonium cation, 4-cyclohexylphenyldiphenylsulfonium cation, 4-methanesulfonylphenyldiphenylsulfonium cation, (4-tert-butoxyphenyl) diphenylsulfonium cation, Bis (4-tert-butoxyphenyl) phenylsulfonium cation, 4-cyclohexylsulfonylphenyldiphenylsulfonium cation and the like are preferable.
  • trisubstituted carbocations such as triphenyl carbocation, tri (methylphenyl) carbocation, and tri (dimethylphenyl) carbocation are preferable.
  • ammonium cation examples include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-diethylanilinium cation, N. , N, N-dialkylanilinium cations such as N-2,4,6-pentamethylanilinium cations; dialkylammonium cations such as di (isopropyl) ammonium cations, dicyclohexylammonium cations and the like are preferred.
  • trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation
  • the phosphonium cation include tetraarylphosphonium cations such as tetraphenylphosphonium cation, tetrakis (methylphenyl) phosphonium cation, and tetrakis (dimethylphenyl) phosphonium cation; and tetraalkylphosphonium cations such as tetrabutylphosphonium cation and tetrapropylphosphonium cation. Etc. are preferable.
  • iodonium cation iodonium cation, carbocation, and sulfonium cation are preferable, and iodonium cation is more preferable, in terms of the film stability of the compound.
  • the iodonium cation as the counter cation of the first ionic compound preferably has a structure represented by the following formula (6).
  • Ar 5 and Ar 6 are each independently an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
  • the aromatic hydrocarbon ring group or aromatic heterocyclic group as Ar 5 and Ar 6 can be selected from the same structures as in the case of Ar 1 , Ar 2 , Ar 3 and Ar 4 , and the preferred structure is also Ar 1 , You can choose from the same structures as for Ar 2 , Ar 3 and Ar 4 .
  • the counter cation represented by the above formula (6) is preferably represented by the following formula (7).
  • Ar 7 and Ar 8 are the same as the substituents that Ar 5 and Ar 6 may have in the above formula (6).
  • the molecular weight of the first ionic compound used in the present invention is usually in the range of 900 or more, preferably 1000 or more, more preferably 1200 or more, and usually 10,000 or less, preferably 5000 or less, still more preferably 3000 or less. .. If the molecular weight is too small, the delocalization of positive and negative charges is insufficient, which may reduce the electron acceptability, and if the molecular weight is too large, the charge transport may be hindered.
  • the compounds of (B-1) and (B-2) are preferable in terms of electron acceptability, heat resistance, and solubility. Further, since it is highly stable as a composition for a charge transport film, (B-18), (B-19), (B-20), (B-21), (B-25), and (B-26). ), (B-28), (B-29) are more preferable, and (B-19), (B-21), (B-25), (B-26), ( B-28) and (B-29) are particularly preferable.
  • the hole injection layer preferably contains a hole transport material, and is preferably formed using the hole transport material.
  • a compound having an ionization potential of 4.5 eV to 5.5 eV is preferable in terms of hole transporting ability.
  • Examples include aromatic amine compounds, phthalocyanine derivatives, porphyrin derivatives, oligothiophene derivatives and the like. Of these, aromatic amine compounds are preferable from the viewpoint of amorphousness, solubility in a solvent, and transmittance of visible light.
  • the aromatic tertiary amine compound is particularly preferable in the present invention.
  • the aromatic tertiary amine compound as used in the present invention includes a compound having an aromatic tertiary amine structure and having a group derived from the aromatic tertiary amine.
  • the type of aromatic tertiary amine compound is not particularly limited, but an aromatic tertiary amine polymer compound which is a polymer compound is preferable.
  • the molecular weight of the polymer compound is preferably 5,000 or more, more preferably 7,000 or more, particularly preferably 10,000 or more, further preferably 1,000,000 or less, further preferably 200,000 or less, and 100,000 or less.
  • a polymer compound having a triphenylamine structure in the main chain is more preferable from the viewpoint of hole transportability.
  • aromatic tertiary amine polymer compound A preferable example of the aromatic tertiary amine polymer compound is a polymer compound having a repeating unit represented by the following formula (11).
  • j 10 , k 10 , l 10 , m 10 , n 10 , and p 10 each independently represent an integer of 0 or more. However, l 10 + m 10 ⁇ 1.
  • Ar 11 , Ar 12 , and Ar 14 each independently represent a divalent aromatic ring group which may have a substituent.
  • Ar 13 represents a divalent aromatic ring group which may have a substituent or a divalent group represented by the following formula (12)
  • Q 11 and Q 12 are independent oxygen atoms, respectively. It represents a hydrocarbon chain having 6 or less carbon atoms which may have a sulfur atom and a substituent, and S 1 to S 4 are each independently represented by a group represented by the following formula (13).
  • the aromatic ring groups of Ar 11 , Ar 12 , and Ar 14 are divalent aromatic hydrocarbon groups which may have a substituent, and divalent aromatic heterocyclic groups which may have a substituent. Alternatively, a plurality of at least two groups selected from a divalent aromatic hydrocarbon group which may have a substituent and a divalent aromatic heterocyclic group which may have a substituent are linked 2 Represents the basis of the value.
  • the aromatic ring group of Ar 11 , Ar 12 , and Ar 14 preferably has 60 or less carbon atoms.
  • the aromatic hydrocarbon group preferably has 6 or more carbon atoms and 30 or less carbon atoms, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, and a chrysene ring.
  • Triphenylene ring, acenaphthene ring, fluorantene ring, fluorene ring and the like, a 6-membered monocyclic ring or a divalent group of a 2-5 fused ring can be mentioned.
  • the aromatic heterocyclic group preferably has 3 or more carbon atoms and 30 or less carbon atoms, and specifically, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, or an oxadiazole ring.
  • a divalent group or a divalent biphenyl group derived from a benzene ring, a naphthalene ring, a fluorene ring, a pyridine ring or a carbazole ring is preferable because of its excellent charge transport property, durability and heat resistance.
  • a divalent group derived from a fluorene ring or a carbazole ring, or a divalent biphenyl group is more preferable.
  • Ar 11 , Ar 12 , and Ar 14 have a divalent benzene ring which may have a substituent, a divalent fluorene ring which may have a substituent, or a substituent.
  • a group selected from a divalent carbazole ring may be used, or a divalent group in which a plurality of two or more rings selected from these structures are linked is preferable, and the aromatic rings of Ar 11 , Ar 12 , and Ar 14 are preferable.
  • the number of carbon atoms of the group is preferably 60 or less.
  • aromatic ring groups may have a substituent, and the substituent that may have can be selected from the substituent group Z.
  • Ar 13 is an aromatic ring group, it is the same as in the case of Ar 11 , Ar 12 , and Ar 14 .
  • Ar 13 is also preferably a divalent group represented by the following formula (12).
  • R 11 represents an alkyl group, an aromatic ring group, or a trivalent group consisting of an alkyl group having 40 or less carbon atoms and an aromatic ring group, which may have a substituent.
  • R 12 represents an alkyl group, an aromatic ring group, or a divalent group consisting of an alkyl group having 40 or less carbon atoms and an aromatic ring group, which may have a substituent.
  • Ar 31 represents a monovalent aromatic ring group or a monovalent cross-linking group, and these groups may have a substituent.
  • the asterisk (*) indicates the bond with the nitrogen atom of the formula (11).
  • aromatic ring group of R 11 examples include a phenyl ring, a naphthalene ring, a carbazole ring, a dibenzofuran ring, a dibenzothiophene ring, and a trivalent group derived from a linked ring having 30 or less carbon atoms linked thereto.
  • alkyl group of R 11 include a trivalent group derived from methane, ethane, propane, isopropane, butane, isobutane, and pentane.
  • aromatic ring group of R 12 examples include a phenyl ring, a naphthalene ring, a carbazole ring, a dibenzofuran ring, a dibenzothiophene ring, and a divalent group derived from a linked ring having 30 or less carbon atoms linked thereto.
  • alkyl group of R12 examples include a divalent group derived from methane, ethane, propane, isopropane, butane, isobutane, and pentane.
  • aromatic ring group of Ar 31 examples include a phenyl ring, a naphthalene ring, a carbazole ring, a dibenzofuran ring, a dibenzothiophene ring, and a monovalent group derived from a linked ring having 30 or less carbon atoms linked thereto.
  • the cross-linking group of Ar 31 is not particularly limited, but is the same as the cross-linking group of the electron-accepting compound having the cross-linking group contained in the hole injection layer of the organic electric field light emitting element of the present invention, and is the same as the cross-linking group of the above formula (X1). )-(X18) is preferable.
  • a group derived from a benzocyclobutene ring, a naphthocyclobutene ring or an oxetane ring, a vinyl group and an acrylic group are preferable.
  • Groups derived from the benzocyclobutene ring or the naphthocyclobutene ring are more preferred because of the stability of the compound.
  • S 1 to S 4 are independent groups represented by the following formula (13).
  • q and r each independently represent an integer of 0 to 6.
  • q and r are each independently preferably preferably 0 to 4, and more preferably 0 or 1.
  • Ar 21 and Ar 23 each independently represent a divalent aromatic ring group, and these groups may have a substituent.
  • Ar 22 represents a monovalent aromatic ring group which may have a substituent
  • R 13 represents an alkyl group, an aromatic ring group or a divalent group consisting of an alkyl group and an aromatic ring group, which are substituted. It may have a group.
  • Ar 32 represents a monovalent aromatic ring group or a monovalent cross-linking group, and these groups may have a substituent.
  • the asterisk (*) indicates a bond with the nitrogen atom of the general formula (11).
  • Examples of the aromatic ring groups of Ar 21 and Ar 23 are the same as those of Ar 11 , Ar 12 , and Ar 14 .
  • the aromatic ring group of Ar 22 and Ar 32 is a monovalent aromatic hydrocarbon group which may have a substituent, a monovalent aromatic heterocyclic group which may have a substituent, or a substituent.
  • the aromatic ring group of Ar 22 and Ar 32 preferably has 60 or less carbon atoms.
  • the aromatic hydrocarbon group preferably has 6 or more carbon atoms and 30 or less carbon atoms, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, and a chrysene ring.
  • Triphenylene ring, acenaphthene ring, fluorantene ring, fluorene ring, etc. 6-membered monocyclic ring or monovalent group of 2-5 fused ring.
  • the aromatic heterocyclic group preferably has 3 or more carbon atoms and 30 or less carbon atoms, and specifically, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, or an oxadiazole ring.
  • a monovalent group or a biphenyl group derived from a benzene ring, a naphthalene ring, a fluorene ring, a pyridine ring or a carbazole ring is preferable because of its excellent charge transport property, durability and heat resistance.
  • aromatic ring groups may have a substituent, and the substituent that may have can be selected from the substituent group Z.
  • Examples of the alkyl group or aromatic ring group of R 13 are the same as those of R 12 .
  • the cross-linking group of Ar 32 is not particularly limited, but is the same as the example of the cross-linking group of Ar 31 , and the preferred example is also the same.
  • All of the above Ar 11 to Ar 14 , R 11 , R 12 , Ar 21 to Ar 23 , Ar 31 to Ar 32 , Q 11 and Q 12 have further substituents as long as they do not contradict the gist of the present invention. May be.
  • the molecular weight of the substituent is usually 400 or less, particularly preferably about 250 or less.
  • the type of the substituent is not particularly limited, and examples thereof include one or more selected from the substituent group Z.
  • the polymer compound having the repeating unit represented by the following formula (14) is preferable because the hole injection / transportability is very high.
  • R 21 to R 25 each independently represent an arbitrary substituent. Specific examples of the substituents of R 21 to R 25 are the same as those of the substituents described in the substituent group Z.
  • Y' represents a divalent aromatic ring group having 30 or less carbon atoms which may have a substituent.
  • aromatic ring group of Y' are the same as in the case of Ar 11 , Ar 12 and Ar 14 described above, and the same is true for the substituents that may be possessed.
  • s and t independently represent integers of 0 or more and 5 or less.
  • u, v, and w each independently represent an integer of 0 or more and 4 or less.
  • Preferred examples of the aromatic tertiary amine polymer compound include a polymer compound containing a repeating unit represented by the following formula (15) and / or formula (16).
  • Ar 45 , Ar 47 and Ar 48 each independently have a monovalent aromatic hydrocarbon group or a substituent which may have a substituent.
  • Ar 44 and Ar 46 each independently represent a divalent aromatic hydrocarbon group which may have a substituent or a divalent aromatic heterocyclic group which may have a substituent.
  • R 41 to R 43 each independently represent a hydrogen atom or an arbitrary substituent.
  • r is an integer of 0 to 2.
  • Ar 44 and Ar 46 preferred examples, examples of substituents that may be possessed, and examples of preferred substituents are independently the same as for Ar 11 and Ar 14 , respectively.
  • R 41 to R 43 are preferably a hydrogen atom or a substituent described in the substituent group Z, and more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an aromatic hydrocarbon group or an aromatic group. It is a group heterocyclic group.
  • R is preferably 0 or 1, and more preferably 0.
  • aromatic amine compound applicable as a hole transport material examples include conventionally known compounds that have been used as a hole injecting / transporting layer-forming material in an organic electroluminescent device.
  • aromatic diamine compound in which a tertiary aromatic amine unit such as 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane is linked Japanese Patent Laid-Open No.
  • the aromatic amine compound applicable as a hole transport material a metal complex of an 8-hydroxyquinoline derivative having a diarylamino group can be mentioned.
  • the central metal is an alkali metal, an alkaline earth metal, Sc, Y, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Al, Ga, In, Si, Ge, Sn. , Sm, Eu, Tb, and the ligand 8-hydroxyquinoline has one or more diarylamino groups as substituents, but may have any substituents other than the diarylamino group. ..
  • porphyrin As a preferable specific example of a phthalocyanine derivative or a porphyrin derivative applicable as a hole transport material, porphyrin, 5,10,15,20-tetraphenyl-21H, 23H-porphyrin, 5,10,15,20-tetra Phthalocyanine-21H, 23H-porphyrin cobalt (II), 5,10,15,20-tetraphenyl-21H, 23H-porphyrin copper (II), 5,10,15,20-tetraphenyl-21H, 23H-porphyrin zinc (II), 5,10,15,20-tetraphenyl-21H, 23H-porphyrin vanadium (IV) oxide, 5,10,15,20-tetra (4-pyridyl) -21H, 23H-porphyrin, 29H, 31H -Pthalocyanine copper (II), phthalocyanine zinc (II), phthalocyanine titanium,
  • oligothiophene derivative applicable as a hole transport material
  • ⁇ -sexthiophene and the like can be mentioned.
  • the molecular weight of these hole transporting materials is usually 5000 or less, preferably 3000 or less, more preferably 2000 or less, still more preferably 1700 or less, except for the above-mentioned polymer compounds having a specific repeating unit. Particularly preferably, it is in the range of 1400 or less, usually 200 or more, preferably 400 or more, and more preferably 600 or more. If the molecular weight of the hole transport material is too large, it is difficult to synthesize and purify it, which is not preferable. On the other hand, if the molecular weight is too small, the heat resistance may be lowered, which is also not preferable.
  • the hole injection layer of the organic electroluminescent device of the present invention may contain any one of the above-mentioned hole transport materials alone, or may contain two or more of them.
  • the hole injection layer contains two or more kinds of hole transporting materials
  • the combination is arbitrary, but one or more kinds of aromatic tertiary amine polymer compounds and one or two other hole transporting materials. It is preferable to use it in combination with seeds or more.
  • an aromatic amine compound is preferable.
  • the content of the hole transporting material in the hole injection layer of the organic electroluminescent device of the present invention shall be within a range satisfying the ratio with the above-mentioned electron accepting compound.
  • the total content of these should be included in the above range.
  • the hole injection layer of the organic electric field light emitting element of the present invention preferably contains a charge-transporting ionic compound in which the tetraarylborate ion and a cation radical of a hole-transporting material are ionically bonded.
  • the hole injection layer of the organic electric field light emitting element of the present invention is a charge-transporting ionic compound in which the tetraarylborate ion and the cation radical of the aromatic tertiary amine polymer compound are ionically bonded as a hole-transporting material. It is particularly preferable to include it.
  • This charge-transporting ionic compound can be obtained by any of the following methods. i) The first ionic compound and the hole transporting material are dissolved or dispersed in an organic solvent and mixed. ii) The first ionic compound and the hole transporting material are dissolved or dispersed in an organic solvent, mixed, and further heated. iii) The composition obtained in the above i) or ii) is wet-formed and the film is heated.
  • the hole transport material is oxidized by the first ionic compound to become a cationic radical by any of the above methods.
  • a charge-transporting ionic compound which is an ionic compound having the tetraarylborate ion as a counter anion and a cation radical of a hole transport material as a counter cation, is produced.
  • the hole injection layer of the organic electric field light emitting element of the present invention preferably contains a first ion compound containing the tetraarylborate ion as a counter anion and a hole transport material, and the tetraarylborate ion is a counter anion. It is more preferable to contain a charge-transporting ionic compound having a cation radical of the hole-transporting material as a counter cation from the viewpoint of charge-transporting property.
  • the hole injection layer of the organic electroluminescent device of the present invention is preferably obtained by wet-forming a composition for forming a hole injection layer.
  • the composition for forming a hole injection layer may be a composition obtained through a step of dissolving or dispersing the first ionic compound having the tetraarylborate ion structure and the hole transporting material in an organic solvent. preferable.
  • the hole injection layer forming composition is preferably a solution in which the first ionic compound and the hole transport material are dissolved in an organic solvent.
  • the composition for forming a hole-injected layer obtained by the method of i) does not contain the charge-transporting ion compound, the charge-transporting ion by the method of ii) or ii). It suffices if a compound can be obtained, and even if the composition for forming a hole injection layer obtained by the method of ii) does not contain the charge-transporting ionic compound, the charge-transporting property is obtained by the method of ii). It suffices if an ionic compound can be obtained.
  • the compounding ratio of the first ionic compound and the hole transport material for obtaining the composition for forming the hole injection layer is such that the amount of the first ionic compound is 100 parts by mass of the hole transport material. It is usually 0.1 part by mass or more, preferably 1 part by mass or more, and usually 100 parts by mass or less, preferably 40 parts by mass or less.
  • the content of the first ionic compound is at least the above lower limit, free carriers (cationic radicals of the hole transport material) can be sufficiently generated, and the hole transportability is improved, which is preferable, and when it is at least the above upper limit. , Sufficient charge transport capacity can be secured, which is preferable.
  • the total content of these compounds should be included in the above range. The same applies to the hole transport material.
  • the concentration of the organic solvent in the composition for forming a hole injection layer is usually 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, and usually 99. It is in the range of .999% by mass or less, preferably 99.99% by mass or less, and more preferably 99.9% by mass or less. When two or more kinds of organic solvents are mixed and used, the total of these organic solvents should satisfy this range.
  • Preferred organic solvents include, for example, ether-based solvents and ester-based solvents.
  • the ether-based solvent include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3.
  • -Aromatic ethers such as dimethoxybenzene, anisole, phenetol, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole and 2,4-dimethylanisole can be mentioned.
  • ester-based solvent examples include aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate, and n-butyl lactate; phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and benzoic acid.
  • aromatic esters such as n-butyl. Any one of these may be used alone, or two or more thereof may be used in any combination and ratio.
  • Examples of the solvent that can be used other than the above-mentioned ether solvent and ester solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene, and amides such as N, N-dimethylformamide and N, N-dimethylacetamide.
  • aromatic hydrocarbon solvents such as benzene, toluene and xylene
  • amides such as N, N-dimethylformamide and N, N-dimethylacetamide.
  • Examples include system solvents, dimethyl sulfoxide and the like. Any one of these may be used alone, or two or more thereof may be used in any combination and ratio. Further, one or more of these solvents may be used in combination with one or more of the above-mentioned ether-based solvents and ester-based solvents.
  • aromatic hydrocarbon-based solvents such as benzene, toluene, and xylene have a low ability to dissolve electron-accepting compounds and free carriers (cationic radicals), so they should be mixed with ether-based solvents and ester-based solvents. preferable.
  • a solvent having an aromatic hydrocarbon structure is more preferable.
  • the hole injection layer can be formed by wet film formation using a composition for forming a hole injection layer.
  • the wet film forming method is the same as the method of forming a light emitting layer forming composition by wet film forming, but it is preferable to heat after coating and drying.
  • the heating temperature is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, more preferably 180 ° C. or higher, still more preferably 300 ° C. or lower, still more preferably 260 ° C. or lower.
  • the hole injection layer can be crosslinked by heating the membrane after coating and drying. At this time, a cross-linking reaction can occur with the following combinations.
  • heating promotes the formation of a charge-transporting ionic compound, which is an ionic compound of tetraarylborate ion, which is a counter anion of the first ionic compound, and a cation radical of a hole-transporting material, which is preferable.
  • a charge-transporting ionic compound which is an ionic compound of tetraarylborate ion, which is a counter anion of the first ionic compound, and a cation radical of a hole-transporting material, which is preferable.
  • FIG. 1 shows a schematic view (cross section) of a structural example of the organic electroluminescent device 8.
  • 1 is a substrate
  • 2 is an anode
  • 3 is a hole injection layer
  • 4 is a hole transport layer
  • 5 is a light emitting layer
  • 6 is an electron transport layer
  • 7 is a cathode.
  • the substrate 1 serves as a support for an organic electric field light emitting element, and usually a quartz or glass plate, a metal plate, a metal foil, a plastic film, a sheet, or the like is used. Of these, a glass plate or a transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, or polysulfone is preferable.
  • the substrate is preferably made of a material having a high gas barrier property because the organic electroluminescent element is unlikely to be deteriorated by the outside air. Therefore, particularly when a material having a low gas barrier property such as a substrate made of synthetic resin is used, it is preferable to provide a dense silicon oxide film or the like on at least one side of the substrate to improve the gas barrier property.
  • the anode 2 has a function of injecting holes into the layer on the light emitting layer 5 side.
  • the anode 2 is usually a metal such as aluminum, gold, silver, nickel, palladium, platinum; a metal oxide such as an oxide of indium and / or tin; a halide metal such as copper iodide; carbon black and poly (3). -Methylthiophene), polypyrrole, polyaniline and other conductive polymers.
  • the anode 2 is usually formed by a dry method such as a sputtering method or a vacuum vapor deposition method.
  • a dry method such as a sputtering method or a vacuum vapor deposition method.
  • metal fine particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, conductive polymer fine powder, etc.
  • an appropriate binder resin solution it can also be formed by dispersing and applying it on a substrate.
  • a conductive polymer a thin film can be formed directly on the substrate by electrolytic polymerization, or an anode can be formed by applying the conductive polymer on the substrate (Appl. Phys. Lett., 60). Volume, p. 2711, 1992).
  • the anode 2 usually has a single-layer structure, but may have a laminated structure as appropriate. When the anode 2 has a laminated structure, different conductive materials may be laminated on the first-layer anode.
  • the thickness of the anode 2 may be determined according to the required transparency and material. When particularly high transparency is required, a thickness having a visible light transmittance of 60% or more is preferable, and a thickness having a visible light transmittance of 80% or more is further preferable.
  • the thickness of the anode 2 is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less.
  • the thickness of the anode 2 may be arbitrarily set according to the required strength and the like, and in this case, the anode 2 may have the same thickness as the substrate.
  • impurities on the anode 2 are removed and the ionization potential thereof is formed by treating the surface of the anode 2 with ultraviolet rays / ozone, oxygen plasma, argon plasma, or the like. It is preferable to improve the hole injection property.
  • the hole injection layer in the organic electroluminescent device of the present invention is as described above.
  • the film forming method of the hole injection layer the wet film forming method is described above, but the vacuum vapor deposition method may be used.
  • the first ionic compound is used as a material containing tetraarylborate ions, and the hole transport material is low, which can be vapor-deposited.
  • a molecular hole transport material can be used.
  • a hole transport material having a molecular weight of 1500 or less is preferable, a hole transport material having a molecular weight of 1000 or less is preferable, and a hole transport material having a molecular weight of 400 or more is preferable, and a hole transport material having a molecular weight of 600 or more is preferable.
  • the above hole transport material is more preferable.
  • an aromatic amine compound is preferable, and an aromatic tertiary amine compound is more preferable.
  • the hole injection layer 3 is formed by the vacuum vapor deposition method
  • a crucible installed in a vacuum vessel (two or more kinds of materials).
  • the crucible is heated (when two or more kinds of materials are used, each crucible is usually heated), and the material in the crucible is evaporated while controlling the evaporation amount (when two or more kinds of materials are used). Evaporates while controlling the amount of evaporation independently) to form a hole injection layer on the anode on the substrate placed facing the crucible.
  • a mixture thereof can be placed in a crucible and heated and evaporated to form a hole injection layer.
  • the degree of vacuum at the time of vapor deposition is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 ⁇ 10 -6 Torr (0.13 ⁇ 10 -4 Pa) or more, 9.0 ⁇ 10 -6 Torr ( 12.0 ⁇ 10 -4 Pa) or less.
  • the vapor deposition rate is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 ⁇ / sec or more and 5.0 ⁇ / sec or less.
  • the film formation temperature at the time of vapor deposition is not limited as long as the effect of the present invention is not significantly impaired, but is preferably 10 ° C. or higher and 50 ° C. or lower.
  • the hole transport layer 4 is a layer having a function of transporting holes from the anode 2 side to the light emitting layer 5 side.
  • the hole transport layer 4 is not an essential layer in the organic electroluminescent device of the present invention, but it is preferable to form this layer in terms of enhancing the function of transporting holes from the anode 2 to the light emitting layer 5. ..
  • the hole transport layer 4 is usually formed between the anode 2 and the light emitting layer 5. Further, when the hole injection layer 3 described above is present, it is formed between the hole injection layer 3 and the light emitting layer 5.
  • the film thickness of the hole transport layer 4 is usually 5 nm or more, preferably 10 nm or more, and on the other hand, usually 300 nm or less, preferably 100 nm or less.
  • the hole transport layer 4 may be formed by either a vacuum vapor deposition method or a wet film deposition method. From the viewpoint of excellent film forming property, it is preferable to form by a wet film forming method.
  • the hole transport layer 4 usually contains a hole transport compound.
  • the hole transporting compound includes two or more tertiary amines represented by 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl and two or more condensed aromatics.
  • Aroma having a starburst structure such as aromatic diamine (Japanese Patent Laid-Open No. 5-234681) in which the ring is substituted with a nitrogen atom, 4,4', 4''-tris (1-naphthylphenylamino) triphenylamine, etc.
  • Group amine compounds J. Lumin., Vol. 72-74, pp. 985, 1997), aromatic amine compounds consisting of triphenylamine tetramers (Chem.
  • hole transport layer is formed by the wet film forming method
  • holes are usually formed instead of the hole injection layer forming composition in the same manner as in the case where the hole injection layer is formed by the wet film forming method. It is formed using a composition for forming a transport layer.
  • the composition for forming the hole transport layer usually further contains a solvent.
  • a solvent used in the composition for forming a hole transport layer, the same solvent as the solvent used in the composition for forming a hole injection layer described above can be used.
  • the concentration of the hole-transporting compound in the composition for forming the hole-transporting layer can be in the same range as the concentration of the hole-transporting compound in the composition for forming the hole-injecting layer.
  • the hole transport is usually performed instead of the composition for forming the hole injection layer in the same manner as in the case of forming the hole injection layer by the vacuum vapor deposition method. It can be formed using a layer-forming composition.
  • the film formation conditions such as the degree of vacuum, the vapor deposition rate, and the temperature at the time of vapor deposition can be the same as those at the time of vacuum deposition of the hole injection layer.
  • the light emitting layer 5 is a layer having a function of emitting light by being excited by recombination of holes injected from the anode 2 and electrons injected from the cathode 7 when an electric field is applied between the pair of electrodes. ..
  • the light emitting layer 5 is a layer formed between the anode 2 and the cathode 7, and the light emitting layer is formed between the hole injection layer and the cathode when there is a hole injection layer on the anode, and the anode. If there is a hole transport layer on top of it, it is formed between the hole transport layer and the cathode.
  • the light emitting layer of the organic electroluminescent device in the present invention preferably contains a polycyclic heterocyclic compound represented by the formula (1) and a host material.
  • the film thickness of the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired. .. Therefore, it is preferably 3 nm or more, more preferably 5 nm or more, and usually 200 nm or less, further preferably 100 nm or less.
  • the light emitting layer 5 contains at least a material having light emitting properties (light emitting material), and preferably contains one or more host materials.
  • a hole blocking layer may be provided between the light emitting layer 5 and the electron injection layer described later.
  • the hole blocking layer is a layer laminated on the light emitting layer 5 so as to be in contact with the interface on the cathode 7 side of the light emitting layer 5.
  • This hole blocking layer has a role of blocking holes moving from the anode 2 from reaching the cathode 7 and a role of efficiently transporting electrons injected from the cathode 7 toward the light emitting layer 5.
  • the physical properties required for the material constituting the hole blocking layer are high electron mobility and low hole mobility, a large energy gap (difference between HOMO and LUMO), and an excited triplet level (T 1 ). Is high.
  • Examples of the material of the hole blocking layer satisfying such conditions include bis (2-methyl-8-quinolinolato) (phenorato) aluminum, bis (2-methyl-8-quinolinolato) (triphenylsilanorat) aluminum and the like.
  • Mixed ligand complex bis (2-methyl-8-quinolato) aluminum- ⁇ -oxo-bis- (2-methyl-8-quinolilato) aluminum dinuclear metal complex and other metal complexes, distyrylbiphenyl derivative and the like.
  • Triazole derivatives such as styryl compounds (Japanese Patent Laid-Open No.
  • the hole blocking layer There are no restrictions on the method of forming the hole blocking layer. Therefore, it can be formed by a wet film forming method, a thin film deposition method, or another method.
  • the film thickness of the hole blocking layer is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less. ..
  • the electron transport layer 6 is provided between the light emitting layer 5 and the cathode 7 for the purpose of further improving the current efficiency of the device.
  • the electron transport layer 6 is formed of a compound capable of efficiently transporting electrons injected from the cathode 7 between electrodes to which an electric field is applied in the direction of the light emitting layer 5.
  • the electron transporting compound used in the electron transporting layer 6 is a compound having high electron injection efficiency from the cathode 7, high electron mobility, and capable of efficiently transporting the injected electrons. is required.
  • the electron-transporting compound used in the electron-transporting layer include a metal complex such as an aluminum complex of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), 10-hydroxybenzo [h].
  • 2-tert-butyl-9,10-N, N'-dicyano examples thereof include anthraquinone diimine, n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, and n-type zinc selenium.
  • the film thickness of the electron transport layer 6 is usually 1 nm or more, preferably 5 nm or more, and usually 300 nm or less, preferably 100 nm or less.
  • the electron transport layer 6 is formed by laminating on the hole blocking layer by a wet film forming method or a vacuum vapor deposition method in the same manner as described above. Usually, a vacuum deposition method is used.
  • the electron injection layer may be provided to efficiently inject the electrons injected from the cathode 7 into the electron transport layer 6 or the light emitting layer 5.
  • the material forming the electron injection layer is preferably a metal having a low work function.
  • alkali metals such as sodium and cesium, alkaline earth metals such as barium and calcium, and the like are used.
  • the film thickness is usually preferably 0.1 nm or more and 5 nm or less.
  • an organic electron transport material represented by a nitrogen-containing heterocyclic compound such as vasophenantroline and a metal complex such as an aluminum complex of 8-hydroxyquinoline is doped with an alkali metal such as sodium, potassium, cesium, lithium and rubidium ().
  • an alkali metal such as sodium, potassium, cesium, lithium and rubidium ().
  • the film thickness of the electron injection layer is usually 5 nm or more, preferably 10 nm or more, and usually 200 nm or less, preferably 100 nm or less.
  • the electron injection layer is formed by laminating on the light emitting layer 5 or the hole blocking layer or the electron transport layer 6 on the light emitting layer 5 by a wet film forming method or a vacuum vapor deposition method.
  • the details of the wet film forming method are the same as those of the above-mentioned light emitting layer.
  • the hole blocking layer, electron transport layer, and electron injection layer are made into one layer by the operation of electron transport material and lithium complex co-doping.
  • the cathode 7 plays a role of injecting electrons into a layer on the light emitting layer 5 side (electron injection layer, light emitting layer, or the like).
  • the material used for the anode 2 can be used, but in order to efficiently inject electrons, it is preferable to use a metal having a low work function, for example, tin and magnesium.
  • a metal having a low work function for example, tin and magnesium.
  • Indium, calcium, aluminum, metals such as silver or alloys thereof are used.
  • Specific examples include alloy electrodes having a low work function such as magnesium-silver alloys, magnesium-indium alloys, and aluminum-lithium alloys.
  • the organic electroluminescent element it is preferable to laminate a metal layer having a high work function and stable with respect to the atmosphere on the cathode to protect the cathode made of a metal having a low work function.
  • the metal to be laminated include metals such as aluminum, silver, copper, nickel, chromium, gold, and platinum.
  • the film thickness of the cathode is usually the same as that of the anode.
  • the organic electroluminescent device of the present invention may further have another layer as long as the effect of the present invention is not significantly impaired. That is, any of the above-mentioned other layers may be provided between the anode and the cathode.
  • the organic electroluminescent device of the present invention has a structure opposite to that described above, that is, for example, a cathode, an electron injection layer, an electron transport layer, a hole blocking layer, a light emitting layer, a hole transport layer, and holes on a substrate. It is also possible to stack the injection layer and the anode in this order.
  • the organic electroluminescent device of the present invention When the organic electroluminescent device of the present invention is applied to an organic electroluminescent device, it may be used as a single organic electroluminescent device or may be used in a configuration in which a plurality of organic electroluminescent devices are arranged in an array.
  • the anode and cathode may be arranged in an XY matrix.
  • the organic EL display device (organic electroluminescent element display device) of the present invention includes the organic electroluminescent element of the present invention.
  • the model and structure of the organic EL display device of the present invention are not particularly limited, and can be assembled according to a conventional method using the organic electroluminescent device of the present invention.
  • the organic EL display device of the present invention can be obtained by a method as described in "Organic EL Display” (Ohmsha, published on August 20, 2004, by Shizushi Tokito, Chihaya Adachi, Hideyuki Murata). Can be formed.
  • the organic EL lighting (organic electroluminescent element lighting) of the present invention includes the organic electroluminescent element of the present invention.
  • the type and structure of the organic EL lighting of the present invention are not particularly limited, and can be assembled according to a conventional method using the organic electroluminescent device of the present invention.
  • Example 1 An organic electroluminescent device was manufactured by the following method. A 2 mm wide stripe of indium tin oxide (ITO) transparent conductive film deposited on a glass substrate to a thickness of 50 nm (a sputtered film product manufactured by Geomatec Co., Ltd.) using ordinary photolithography technology and hydrochloric acid etching. The anode was formed by patterning. The substrate on which the ITO pattern is formed is washed in the order of ultrasonic cleaning with an aqueous solution of a surfactant, water washing with ultrapure water, ultrasonic cleaning with ultrapure water, and water washing with ultrapure water, and then dried with compressed air. Finally, UV ozone cleaning was performed.
  • ITO indium tin oxide
  • composition for forming the hole injection layer 3.0% by mass of the hole transporting polymer compound having the repeating structure of the following formula (P-1) and 0.6% by mass of the electron accepting compound (HI-1). And was dissolved in ethyl benzoate to prepare a solution.
  • This solution was spin-coated on the substrate in the atmosphere and dried on an atmospheric hot plate at 240 ° C. for 30 minutes to form a uniform thin film having a film thickness of 40 nm to form a hole injection layer.
  • This solution is spin-coated in a nitrogen glove box on a substrate coated with the hole injection layer and dried at 230 ° C. for 30 minutes on a hot plate in the nitrogen glove box to form a uniform thin film having a film thickness of 40 nm. It was formed and used as a hole transport layer.
  • This solution was spin-coated in a nitrogen glove box on a substrate coated with the hole transport layer and dried at 120 ° C. for 20 minutes on a hot plate in the nitrogen glove box to form a uniform thin film having a film thickness of 40 nm. It was formed and used as a light emitting layer.
  • the substrate on which the film was formed up to the light emitting layer was installed in a vacuum vapor deposition apparatus, and the inside of the apparatus was exhausted until it became 2 ⁇ 10 -4 Pa or less.
  • a 2 mm wide striped shadow mask as a mask for cathode vapor deposition is brought into close contact with the substrate so as to be orthogonal to the ITO stripe of the anode, and aluminum is heated by a molybdenum boat to form an aluminum layer having a thickness of 80 nm. Formed to form a cathode.
  • an organic electroluminescent device having a light emitting area portion having a size of 2 mm ⁇ 2 mm was obtained.
  • Example 1 Same as in Example 1 except that the composition for forming a hole injection layer was prepared by using 0.3% by mass of tetracyanoquinodimethane instead of 0.6% by mass of the electron-accepting compound (HI-1). To produce an organic electroluminescent device.
  • Table 1 shows the voltage difference (V) obtained by subtracting the voltage of Comparative Example 1 from the voltage of Example 1 and the relative life of Example 1 when the life of Comparative Example 1 is 1.
  • the organic electroluminescent device of the present invention has a low drive voltage and a long drive life.
  • Example 2 An organic electroluminescent device was produced in the same manner as in Example 1 except that the hole injection layer was formed by using an electron accepting compound (HI-2) instead of the electron accepting compound (HI-1).
  • HI-2 an electron accepting compound
  • Table 2 shows the voltage difference (V) obtained by subtracting the voltage of Example 1 from the voltage of Example 2, the relative current emission efficiency of Example 2 when the current emission efficiency of Example 1 is 1, and the relative current emission efficiency of Example 1.
  • V voltage difference
  • EQE external quantum efficiency
  • Table 2 shows the voltage difference (V) obtained by subtracting the voltage of Example 1 from the voltage of Example 2, the relative current emission efficiency of Example 2 when the current emission efficiency of Example 1 is 1, and the relative current emission efficiency of Example 1.
  • the hole injection layer has a crosslinked product of an electron-accepting compound having a crosslinking group, so that the driving voltage is low, the luminous efficiency is high, and the driving life is long.
  • Example 3 The process up to the formation of the hole injection layer was carried out in the same manner as in Example 1. Next, as the material of the hole transport layer, a compound represented by the following formula (HT-2) is used instead of the compound represented by the above formula (HT-1), and the same as in Example 1 is positive. A hole transport layer was formed.
  • the compound represented by the following formula (H-2) is 22.5 parts by mass
  • the compound represented by the following formula (H-3) is 22.5 parts by mass
  • the following formula ( Weigh 15.0 parts by mass of the compound represented by H-4) and 3.0 parts by mass of the compound represented by the following formula (D-2) dissolve in cyclohexylbenzene, and prepare a 4.2% by mass solution. It was prepared, a light emitting layer was formed in the same manner as in Example 1, and an organic electric field light emitting element was manufactured in the same manner as in Example 1 in the subsequent steps.
  • Example 4 An organic electroluminescent device was used in the same manner as in Example 3, except that the composition for forming a hole injection layer was prepared by using an electron-accepting compound (HI-3) instead of the electron-accepting compound (HI-1). Made.
  • Example 5 An organic electroluminescent device was used in the same manner as in Example 3, except that the composition for forming a hole injection layer was prepared by using an electron-accepting compound (HI-2) instead of the electron-accepting compound (HI-1). Made.
  • Example 6 As the material of the hole transport layer, the compound represented by the formula (HT-1) is used instead of the compound represented by the formula (HT-2), and the compound represented by the formula (HT-1) is used in the material of the light emitting layer.
  • An organic electroluminescent device was produced in the same manner as in Example 5 except that the compound represented by the following formula (D-3) was used instead of the compound represented by -2).
  • Example 2 An organic electroluminescent device was used in the same manner as in Example 3, except that the composition for forming a hole injection layer was prepared by using an electron-accepting compound (HI-C1) instead of the electron-accepting compound (HI-1). Made.
  • HI-C1 an electron-accepting compound
  • Table 3 shows the relative life of each example when the life of Comparative Example 2 is 1. Further, Table 4 shows the relative current luminous efficiency of Examples 4 to 6 when the current luminous efficiency of Example 3 is 1, and Examples 4 to 4 when the external quantum efficiency (EQE) of Example 3 is 1. The relative EQ of 6 is described.
  • the organic electroluminescent device having a hole injection layer used in the present invention has a long drive life, and further, the hole injection layer has a crosslinked product of an electron-accepting compound having a crosslinking group. It was found that the drive life was long.
  • Example 7 The process up to the formation of the hole transport layer was carried out in the same manner as in Example 3. After the formation of the light emitting layer, an organic electroluminescent device was produced in the same manner as in Example 1.
  • Example 8 An organic electroluminescent device was used in the same manner as in Example 7, except that the composition for forming a hole injection layer was prepared by using an electron-accepting compound (HI-3) instead of the electron-accepting compound (HI-1). Made.
  • Comparative Example 5 An organic electroluminescent device was used in the same manner as in Comparative Example 4, except that the composition for forming a hole injection layer was prepared by using an electron-accepting compound (HI-3) instead of the electron-accepting compound (HI-1). Made.
  • Comparative Example 6 An organic electroluminescent device was used in the same manner as in Comparative Example 4, except that the composition for forming a hole injection layer was prepared by using an electron-accepting compound (HI-C1) instead of the electron-accepting compound (HI-1). Made.
  • HI-C1 an electron-accepting compound
  • the light emitting layer is a light emitting layer containing the polycyclic heterocyclic compound of the above formula (1)
  • the organic electroluminescent element having a hole injection layer containing an electron accepting compound used in the present invention the voltage is applied. Is low, the current emission efficiency is high, the EQE is high, and the life is long, but this is not always the case or the degree is low when the light emitting layer is an organic electroluminescent element which is a conventional phosphorescent light emitting layer. The peculiar effect of is confirmed.

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PCT/JP2021/047865 2020-12-23 2021-12-23 有機電界発光素子、有機ｅｌ表示装置、有機ｅｌ照明及び有機電界発光素子の製造方法 WO2022138822A1 (ja)

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WO2024048692A1 (ja) * 2022-08-31 2024-03-07 三菱ケミカル株式会社 発光層用材料、有機電界発光素子、有機ｅｌ表示装置、有機ｅｌ照明、組成物、及び、有機電界発光素子の製造方法

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